Oxazolidone functional compounds and coating compositions including oxazolidone functional compounds

Abstract

Oxazolidone compounds which may be used as additives in coating compositions, coating compositions including such additives, and their use in electrocoat, powder, packaging, and liquid coating applications, and articles coated with the same are disclosed.

Description

OXAZOLIDONE FUNCTIONAL COMPOUNDS AND COATING COMPOSITIONS INCLUDING OXAZOLIDONE FUNCTIONAL COMPOUNDSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit under 35 U.S.C. § 1 19(e) of U.S. Provisional Application No. 63 / 504,319 entitled “OXAZOLIDONE FUNCTIONAL COMPOUNDS AND COATING COMPOSITIONS INCLUDING OXAZOLIDONE FUNCTIONAL COMPOUNDS”, filed on May 25th, 2023, which is incorporated by reference in its entirety.FIELD

[0002] The present disclosure relates to oxazolidone functional compounds, coating compositions including oxazolidone functional compounds, and methods for making and applying such coating compositions.BACKGROUND

[0003] Coating compositions are used to impart a wide variety of functions to substrates, for example, packages for food and beverage products, as well as protective, decorative and / or functional coatings for electronic products, construction products, automotive products, medical / pharmaceutical products, and cosmetic products.

[0004] Coating compositions generally include one or more film-forming components or binders such as natural or synthetic polymers (e.g., latex or polyethylene), waxes, and resins which may self-cure and / or react with a curing agent. Coating compositions may also comprise one or more additives, solvents, pigments, or fillers which improve the characteristics of the coating.SUMMARY

[0005] In one form thereof, the present disclosure provides a method for synthesizing an oxazolidone compound according to Formula (I):wherein R is a connective group comprising a polyether, polyester, polyurethane, alkyl, or aromatic functional group; Ri is a terminal group comprising an epoxy, acid, hydroxyl, or amine containing group, or a non-functional group; R2 is a connective group comprising an aromatic functional group or an aliphatic functional group; and n is from 1 to 500; the method comprising: (i) reacting an isocyanate compound and an epoxy compound in the presence of a catalyst to produce a first product comprising at least two oxazolidone functional group linked by R and comprising linking groups R2; and (ii) reacting the first product with a further compound to provide R1 end groups and produce a second product.

[0006] In another form thereof, the present disclosure provides a composition comprising an oxazolidone functional compound according to Formula (I):wherein R is a connective group comprising a polyether, polyester, polyurethane, alkyl, or aromatic functional group; R1 is a terminal group comprising an epoxy, acid, hydroxyl, or amine containing group, or a non-functional group; R2 is a connective group comprising an aromatic functional group or an aliphatic functional group; and n is from 1 to 500.

[0007] In another form thereof, the present disclosure provides an electrocoat composition comprising: a cationic film forming resin; and an additive compound comprising at least two oxazolidone functionalities, wherein the additive compound has two terminal groups each comprising an amine group, and the additive compound is free of epoxy groups.

[0008] In another form thereof, the present disclosure provides a powder coating composition comprising: a film forming resin; and an additive compoundcomprising at least two oxazolidone functionalities separated by a linking group, wherein the linking group is an aromatic functional group.

[0009] In another form thereof, the present disclosure provides a liquid coating composition, comprising: a polyester resin; and an additive compound comprising two oxazolidone functionalities and at least two terminal groups comprising, and independently selected from, at least one of, an epoxy group an acid group, a hydroxyl group, an amine group, an aromatic group, and an aliphatic group.

[0010] In another form thereof, the present disclosure provides a packaging coating composition comprising: a film forming resin comprising a polyester resin, an acrylic modified polyester, an acrylic resin or a combination thereof; and an additive compound comprising: at least two oxazolidone functionalities; at least two connective groups comprising an aliphatic group; and two terminal groups comprising an epoxy group.DETAILED DESCRIPTIONIntroduction

[0011] Oxazolidones are a class of organic compounds that have been used in various applications such as building blocks in pharmaceuticals and monomers in the production of polymer compositions. The structure of one of the simplest oxazolidones, 2-oxazolidone, is shown below.

[0012] The present disclosure provides a series of coating compositions which comprise oxazolidone functional compounds, namely, compounds that include one or more oxazolidone functional groups, as resins or as additives in coating formulations. These oxazolidone functional compounds may be oligomers or polymers. The oxazolidone compounds may provide improved chemical resistance, hardness, and scratch resistance. They can be used in a variety of coating compositions including solvent-based, water-based, and powder coatings.

[0013] One of the advantages of using oxazolidones in coating compositions is their versatility. They can be used in combination with a wide variety of coatings, curing agents, and resins depending on the requirements of the specific application. Additionally, oxazolidone functional compounds are often low-VOC, which makes then an attractive option for environmentally friendly coating compositions.Definitions

[0014] For purposes of the following detailed description, it is to be understood that the disclosure may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term “about”. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0015] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard variation found in their respective testing measurements.

[0016] Also, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of “1 to 10” is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.

[0017] In this application, the use of the singular includes the plural and plural encompasses singular, unless specifically stated otherwise. In addition, in thisapplication, the use of “or” means “and / or” unless specifically stated otherwise, even though “and / or” may be explicitly used in certain instances. Further, in this application, the use of “a” or “an” means “at least one” unless specifically stated otherwise. For example, “a” polymer, “a” pigment, “a” composition, “a” powder coating composition, “an” effect pigment, “a” polymeric resin particle, and the like refer to one or more of any of these items.

[0018] “Polymer” refers to oligomers, homopolymers (e.g., prepared form a single monomer species), copolymers (e.g., prepared form at least two monomer species), terpolymers (e.g., prepared from at least three monomer species), and graft polymers.

[0019] “Film forming resin” refers to a resin that may form a self-supporting continuous film on at least a horizontal surface of a substrate upon removal or any diluents or carriers.

[0020] "Crosslinker" refers to a molecule comprising two or more functional groups that are reactive with other functional groups and that is capable of linking two or more monomers or polymers through chemical bonds.

[0021] “Cationic electrodepositable binder” or “cationic film forming resin” refers to an organic resinous polymer that includes cationic groups (that may be at least partially neutralized to form cationic salt groups) that impart a positive charge to the polymer and that enable the polymer to be deposited onto a conductive substrate by a cationic electrodeposition process.

[0022] “Colorants” refers to a pigment, tint, dye, or any other coloring material which is used to impart color or opacity to the powder coating composition per ASTM E284. As used herein, the term “colorant” differs from effect pigments.

[0023] “Substantially free of” as used herein indicates that the composition contains the material in question in an amount of 0.5 wt.% or less, based on the entire weight of the composition.

[0024] “Low-VOC” as used herein indicates that the composition has a volatile organic compound (VOC) content of less than 45 g / L calculated according to EPA Method 24.I. Synthesis

[0025] The oxazolidone compounds of the present disclosure may be synthesized via a multistage procedure comprising a first stage of synthesizing the oxazolidone functional adducts and an optional second stage of adding functional groups to the first stage.

[0026] The oxazolidone compounds produced by the synthesis as described herein may have the following Formula (I):wherein each R independently is a connective group comprising a polyether, polyester, polyurethane, alkyl, or aromatic functional group; each Ri independently is a terminal group comprising an epoxy, acid, hydroxyl, carbamate or amine containing group, or a non-functional group; each R2 independently is a connective group comprising an aromatic functional group or an aliphatic functional group; and n is from 1 to 500. Each R, R1, and R2 may be the same or different in Formula (I)

[0027] The first stage of the synthesis may comprise reacting an isocyanate compound and an epoxy compound in the presence of a catalyst to produce a first product. This first product may comprise at least two oxazolidone functional groups linked by R and comprising connective groups R2.

[0028] The second stage of the synthesis may comprise reacting the first product with a further compound to provide R1 end groups to produce a second product. The further compounds in the second group, moiety, or the like may be any group containing a functional group.

[0029] In the first stage, the oxazolidone compounds may be synthesized from a reaction of aliphatic epoxy compounds, aromatic epoxy compounds, and diisocyanates or isocyanate prepolymers in the presence of a catalyst.

[0030] Aliphatic epoxy compounds include any compound which comprises an aliphatic functional group and an epoxy functional group. Aromatic epoxy compounds include any compound which comprises an aromatic functional group and an epoxy functional group.

[0031] Suitable aliphatic and aromatic epoxy compounds include reaction products of a glycidyl ether, such as epichlorohydrin, and a bisphenol compoundsuch as bisphenol A. Also suitable are C4-C28 alkyl glycidyl ethers; C2-C28 alkyland alkenyl-glycidyl esters; C1-C28 alkyl-, mono- and poly-phenol glycidyl ethers; polyglycidyl ethers of pyrocatechol, resorcinol, hydroquinone, 4,4'-dihydroxydiphenyl methane (or bisphenol F), 4,4'-dihydroxy-3,3'-dimethyldiphenyl methane, 4,4'- dihydroxydiphenyl dimethyl methane (or bisphenol A), 4,4'-dihydroxydiphenyl methyl methane, 4,4'-dihydroxydiphenyl cyclohexane, 4,4'-dihydroxy-3,3'-dimethyldiphenyl propane, 4,4'-dihydroxydiphenyl sulfone, and tris (4-hydroxyphynyl)methane; polyglycidyl ethers of the chlorination and bromination products of the above- mentioned diphenols; polyglycidyl ethers of novolacs; polyglycidyl ethers of diphenols obtained by esterifying ethers of diphenols obtained by esterifying salts of an aromatic hydrocarboxylic acid with a dihaloalkane or dihalogen dialkyl ether; polyglycidyl ethers of polyphenols obtained by condensing phenols and long-chain halogen paraffins containing at least two halogen atoms; N,N'-diglycidyl-aniline; N,N'- dimethyl-N,N'-diglycidyl-4,4'-diaminodiphenyl methane; N,N,N',N’-tetraglycidyl-4,4'- diaminodiphenyl methane; N,N’-diglycidyl-4-aminophenyl glycidyl ether; N,N,N',N'- tetraglycidyl-1 ,3-propylene bis-4-aminobenzoate; phenol novolac epoxy resin; cresol novolac epoxy resin; and combinations thereof. Commercially available epoxy resins that can be used in the practice of this invention include but are not limited to Aralydyte GY6010 available from Krayden, Epon 828 available from Hexion Specialty Chemicals, Eponex 1510 available from Hexion Specialty Chemicals, and TSR-400 available from Hexion Specialty Chemicals.

[0032] The diisocyanate is an isocyanate compound with two NCO groups per molecule. Suitable diisocyanate compounds include tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), 2-methylpentamethylene diisocyanate, 2,2,4- trimethyl-hexamethylene diisocyanate (THDI), dodecanemethylene diisocyanate, 1 ,4- diisocyanatocyclohexane, 3-isocyanatomethyl-3,3,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), diisocyanatodicyclohexylmethane (H12- MDI), diphenylmethane diisocyanate (MDI), 4,4’-diisocyanato-3,3’- dimethyldicyclohexylmethane, 4,4'-diisocyanato-2,2- dicyclohexylpropane, poly(hexamethylene diisocyanate), octamethylene diisocyanate, tolylene-alpha,4- diisocyanate, polypropylene glycol) tolylene-2,4-diisocyanate terminated, polyethylene adipate) tolylene-2,4-diisocyanate terminated, 2,4,6-trimethyl-1 ,3- phenylene diisocyanate, 4-chloro-6- methyl-1 ,3-phenylene diisocyanate, poly[1 ,4-phenylene diisocyanate-co-poly(l14-butanediol)] diisocyanate, polytetrafluoroethylene oxide-co-difluoromethylene oxide) a, co- diisocyanate, 1 ,4- diisocanatobutane, 1 ,8-diisocyanatooctane, 1 ,3-bis(l-isocyanato-1 - methylethyl)benzene, 3,3'- dimethyl-4,4'-biphenylene diisocyanate, naphthalene- 1 ,5-diisocyanate, 1 ,3-phenylene diisocyanate, 1 ,4-diisocyanatobenzene, 2,4- or 2,5- or 2,6-diisocyanatotoluene (TDI) or mixtures of these isomers, 4,4'-, 2,4- or 2,2'- diisocyanatodiphenylmethane or mixtures of these isomers, 4,4-, 2,4'- or 2,2'- diisocyanato-2,2-diphenylpropane-p-xylene diisocyanate and a,a,a',a'-tetramethyl- m- or -p- xylene diisocyanate (TMXDI), mixtures thereof or biurets, isocyanurates, carbamates or uretdiones of the aforementioned isocyanates.

[0033] Isocyanate-terminated pre-polymers may also be used in the reaction as a source of NCO groups. These pre-polymers may be prepared by reacting an excess of polyisocyanate with a polyol or an alcohol in the presence of a urethane catalyst. Urethane catalysts are capable of catalyzing the formation of carbamate bonds.

[0034] Polyisocyanates and diisocyanates suitable for the preparation of the isocyanate pre-polymers include but are not limited to the alkylene isocyanates, such as trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (“HDI”), 1 ,2-propylene diisocyanate, 1 ,2- butylene diisocyanate, 2,3-butylene diisocyanate, 1 ,3-butylene diisocyanate, ethylidene diisocyanate, and butylidene diisocyanate, and cycloalkylene isocyanates, such as 1 ,3-cyclopentane diisocyanate, 1 ,4-cyclohexane diisocyanate, 1 ,2- cyclohexane diisocyanate, isophorone diisocyanate, methylene bis(4- cyclohexylisocyanate) (“HMDI”), the cyclo-trimer of 1 ,6-hexmethylene diisocyanate (also known as the isocyanurate trimer of HDI, commercially available as Desmodur N3300 from Convestro AG), and meta-tetramethylxylylene diisocyanate (commercially available as TMXDI® from Allnex SA). Aromatic polyisocyanates may also be used which include (i) arylene isocyanates, such as m-phenylene diisocyanate, p-phenylene diisocyanate, 1 ,5-naphthalene diisocyanate and 1 ,4- naphthalene diisocyanate, and (ii) alkarylene isocyanates, such as 4,4'-diphenylene methane (“MDI”), 2,4-tolylene or 2,6-tolylene diisocyanate (“TDI”), or mixtures thereof, 4,4-toluidine diisocyanate and xylylene diisocyanate. Triisocyanates, such as triphenyl methane-4,4',4"-triisocyanate, 1 ,3,5-triisocyanato benzene and 2,4,6-triisocyanato toluene, tetraisocyanates, such as 4,4'-diphenyldimethyl methane- 2,2',5,5'-tetraisocyanate, and polymerized polyisocyanates, such as tolylene diisocyanate dimers and trimers and the like, may also be used. Suitable polyisocyanates also include blocked polyisocyanates selected from a polymeric polyisocyanate, such as polymeric HDI, polymeric MDI, polymeric isophorone diisocyanate, and the like. The polyisocyanate may also be a blocked trimer of hexamethylene diisocyanate available as Desmodur N3300® from Covestro AG. Mixtures of the foregoing polyisocyanates may also be used.

[0035] The polyols used for the preparation of the isocyanate prepolymer can include but are not limited to any material that contains a reactive hydrogen atom and that would react with the isocyanate or isocyanurate group. These materials include hydroxyl functional acrylics, hydroxyl functional polyesters, hydroxy functional polyethers, polyamines, polyamides, short oil alkyds, caster oil, epoxy resins with secondary hydroxyl groups, phenolic resins, and hydroxyl functional vinyl resins. Suitable polyols include ethylene glycol, propylene glycol, butylene glycol, 1 ,6-hexylene glycol, neopentyl glycol, diethylene glycol, glycerol, trimethylol propane and pentaerythritol. Suitable polyols also include poly(tetrahydrofuran).

[0036] The alcohols suitable for the preparation of the isocyanate prepolymer include but are not limited to aliphatic, cycloaliphatic, or aromatic alkyl monoalcohols or phenolic compounds, including, for example, lower aliphatic alcohols, such as methanol, ethanol, and n-butanol; cycloaliphatic alcohols, such as cyclohexanol; aromatic-alkyl alcohols, such as phenyl carbinol and methylphenyl carbinol; and phenolic compounds, such as phenol itself and substituted phenols wherein the substituents do not affect coating operations, such as cresol and nitrophenol.

[0037] The polyurethane catalyst suitable for the preparation of the isocyanate prepolymer may be any known polyurethane catalyst such as organic tin compounds or amine catalyst. Suitable catalysts include dibutyltin dilaurate, dibutyltin diacetate, diethyltin diacetate, dihexyltin diacetate, di-2-ethylhexyltin oxide, dioctyltin dioxide, stannous octoate, stannous oleate, or a mixture thereof.

[0038] The synthesis of the isocyanate pre-polymer may involve reacting an excess of the polyisocyanate with a polyol or alcohol at a temperature as low as 60°C, 65°C, 70°C, or as high as 75°C, 80°C, 85°C, 90°C, or within any range encompassed by any two of the foregoing values as endpoints. For example, thereaction may be conducted at a temperature of from 60°C to 90°C, 65°C to 85°C, or 70°C to 80°C. During the reaction, the polyol or alcohol may be added slowly into the reaction mixture, such as over a time period of 1 hour or 2 hours.

[0039] Suitable catalysts for the first stage of the oxazolidone synthesis include Lewis Acid catalysts such as phosphonium salts or metal ion complexes. A particularly suitable catalyst is tetrabutylphosphonium bromide. Other suitable catalysts include but are not limited to lithium compounds such as lithium chloride and butoxylithium; boron trifluoride complex salts; quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, and tetramethylammonium iodide; tertiary amines such as dimethylaminoethanol, triethylamine, tributylamine, benzyldimethylamine, and N-methylmorpholine; phosphines such as triphenylphosphine; phosphonium compounds such as allyltriphenylphosphonium bromide, diallyldiphenylphosphonium bromide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium iodide, tetrabutylphosphonium acetate-acetic acid complexes, tetrabutylphosphonium acetate, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, and tetrabutylphosphonium iodide; the combination of triphenylantimony and iodine; and imidazols such as 2-phenylimidazol and 2-methylimidazol. The catalysts listed above may be used singly or in combination of two or more thereof. The catalyst may be present in an amount as low as 20 ppm, 30 ppm, 40 ppm, 50 ppm, 60 ppm, 70 ppm, 80 ppm, 90 ppm, 100 ppm, 200 ppm, 300 ppm, 400 ppm, 500 ppm, 600 ppm, 700 ppm, 800 ppm, 900 ppm, 1000 ppm, 2000 ppm, 3000 ppm, 4000 ppm, 5000 ppm, 6000 ppm, 7000 ppm, 8000 ppm, 9000 ppm, 10,000 ppm, or within any range encompassed by any two of the foregoing values as endpoints, based upon the total weight of the reagents in the first stage of the synthesis. For example, the catalyst may be present in an amount of from 20 ppm to 5000 ppm. 30 ppm to 9000 ppm, 50 ppm to 7000 ppm, 90 ppm to 5000 ppm, 100 ppm to 4000 ppm. Or from 500 ppm to 1000 ppm.

[0040] The first stage of the oxazolidone compound synthesis may involve charging a reaction vessel with the aliphatic or aromatic epoxy compound, diioscyanates or isocyanate pre-polymer, and a catalyst.

[0041] The reaction may be carried out in a reactor that uses a sufficient level of agitation to create a homogenous reaction mixture. Suitable agitation can beachieved by using a mechanical stirrer. The reactor vessel may be coupled to a heating medium to maintain an appropriate reaction temperature. The reactor vessel may be coupled to a cooling bath with any suitable cooling medium to maintain a suitable reaction temperature. The reactor vessel may also be sealed to create a high-pressure environment for conducting the reaction.

[0042] The reaction may be carried out at a temperature as low as 80°C, 90°C, 100°C, 110°C, 120°C, or as high as 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, or within any range encompassed by any two of the foregoing values as endpoints. For example, the reaction may be carried out at a temperature of 100°C to 180°C, 120°C to 180°C, 130°C to 170°C, or 140°C to 160°C.

[0043] The second stage of the oxazolidone synthesis may be used to add a functionality to the oxazolidone compound from the first stage such as an acid, hydroxyl, or amine group. The reaction involves adding a carboxylic acid functional compound or amine compound to the first stage adducts to form hydroxyl or amine functional oxazolidones. Suitable carboxylic acid functional compounds include adipic acid. The formed hydroxyl functional oxazolidones can be further converted to acid functional oxazolidones by reacting hydroxyl group with anhydride compounds. Suitable anhydride compounds include cyclic dicarboxylic anhydrides such as methylhexahydrophthalic anhydride (MHHPA).

[0044] Prior to the second stage of the synthesis, the oxazolidone compounds from the first stage may be acid-functionalized using carboxylic acid functional compounds such as adipic acid.

[0045] The second stage of the synthesis can include heating a mixture of the first stage adducts and a monoisocyanate compounds to further converting epoxy to oxazolidones by using same reaction conditions as first stage.II. Compositions Including Oxazolidone Functional Compounds

[0046] The present disclosure provides an oxazolidone compound and / or a resin composition including a compound according to the following Formula (I): Formula (I)

[0047] In Formula (I), each R may independently be a polyether, polyester, polyurethane, alkyl, or aromatic group; each value for Ri may independently be an epoxy, acid, hydroxyl, carbamate, or amine containing group, or a non-functional group; each R2 may independently contain an aromatic or aliphatic functional group; and n may be 1 , 2, 3, 4, 5, or any integer up to 500, inclusive of 1 , 500, and all integers therebetween, as well as any range including any two of such integers as endpoints. The values for R, R1, and R2 may be the same or different.

[0048] Suitable aromatic containing moieties include divalent moieties having functional groups such as phenyl, tolyl, aniline, nitrobenzene, chlorobenzene, hydroxybenzene, methoxybenzene, ethoxybenzene acetophenone, phenol, 1 ,1 ,3,- trimethylcyclohexane, and 4,4’-(propane-2,2-diyl)bis(methoxybenzene).

[0049] Suitable alkyl or aliphatic groups include any linear or branched C2 to C30 group, inclusive of C2, C30, and all integers therebetween, as well as any range including any two of such integers as endpoints.

[0050] The resin compositions may also be substantially free from epoxy groups.

[0051] The resin compositions may also be substantially free from crosslinking agents such as phenolic crosslinkers, amine based crosslinkers, isocyanates, sulfur- containing compounds such as mercaptans and thiols, and the like.

[0052] The resin compositions may have a weight / number average molecular weight as low as 400 g / mol, 500 g / mol, 600 g / mol, 700 g / mol, 800 g / mol, 900 g / mol, 1000 g / mol, 2000 g / mol, 3000 g / mol, or as high as 4000 g / mol, 5000 g / mol, 6000 g / mol, 7000 g / mol, 8000 g / mol, 9000 g / mol, 10,000 g / mol, or within any range encompassed by any two of the foregoing values as endpoints. For example, the resin compositions may have a weight / number average molecular weight of from 400 g / mol to 10,000 g / mol, 500 g / mol to 8000 g / mol, 1000 g / mol to 7000 g / mol, 2000 g / mol to 6000 g / mol, or 3000 g / mol to 5000 g / mol determined as described below.

[0053] As discussed below, the present oxazolidone compounds may be formulated into a number of coating compositions for various end-use applications,such as E-coats, powder coatings, liquid and coil coating compositions, and packaging coatings.

[0054] Oxazolidone functional compounds are provided below.IV. E-Coat Compositions

[0055] Electrodeposition as a coating application method involves deposition of a film-forming composition onto a conductive substrate under the influence of an applied electrical potential. Electrodeposition has become standard in the coatings industry because, by comparison with non-electrophoretic coating means, electrodeposition offers increased paint utilization with less waste, improved corrosion protection to the substrate, and minimal environmental contamination.

[0056] The present disclosure provides an electrodepositable coating (electrocoat or E-coat) composition which comprises a cationic electrodepositable binder.

[0057] The present disclosure provides an electrocoat composition comprising a cationic film forming resin and an additive comprising oxazolidone functionalities. The electrocoat composition may also include an optional curing agent.

[0058] As stated above, the cationic electrodepositable binder comprises a cationic salt group-containing film-forming polymer. The cationic salt group- containing film-forming polymer may be used in a cationic electrodepositable coating composition. As used herein, the term “cationic salt group-containing film-forming polymer” refers to polymers that include at least partially neutralized cationic groups, such as sulfonium groups, ammonium groups, or phosphonium groups, that impart a positive charge.

[0059] The cationic salt group-containing film-forming polymer comprises functional groups. The functional groups of the cationic salt group-containing filmforming polymer may comprise active hydrogen functional groups. The term “active hydrogen” refers to hydrogens which, because of their position in the molecule, display activity according to the Zerewitinoff test, as described in the JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Vol. 49, page 3181 (1927). Accordingly, active hydrogens include hydrogen atoms attached to oxygen, nitrogen, or sulfur, and thus useful compounds will include those having at least two hydroxyl, thiol, primary amine, and / or secondary amine groups (in any combination). Cationic salt group-containing film-forming polymers that comprise active hydrogen functional groups may be referred to as active hydrogen-containing, cationic salt group- containing film-forming polymers.

[0060] Polymers that are suitable for use as the cationic salt group-containing film-forming polymer in the present invention include, but are not limited to, alkyd polymers, acrylics, polyepoxides, polyamides, polyurethanes, polyureas, polyethers, and polyesters, among others.

[0061] More specific suitable active hydrogen-containing, cationic salt group containing film-forming polymers include polyepoxide-amine adducts, such as the adduct of a polyglycidyl ethers of a polyphenol, such as Bisphenol A, and primary and / or secondary amines. A portion of the amine that is reacted with the polyepoxidemay be a ketimine of a polyamine. Also suitable are ungelled polyepoxidepolyoxyalkylenepolyamine resins. In addition, cationic acrylic resins may be used.

[0062] Besides amine salt group-containing resins, quaternary ammonium salt group-containing resins may also be employed as a cationic salt group-containing film-forming polymer in the present invention. These resins include those which are formed from reacting an organic polyepoxide with a tertiary amine acid salt.

[0063] Other suitable cationic resins include ternary sulfonium salt group- containing resins. Also, cationic resins which cure via a transesterification mechanism, may also be employed.

[0064] Other suitable cationic salt group-containing film-forming polymers include those that may form photodegradation resistant electrodepositable coating compositions. Such polymers include the polymers comprising cationic amine salt groups which are derived from pendant and / or terminal amino groups. Also suitable are the active hydrogen-containing, cationic salt group-containing resins derived from a polyglycidyl ether of a polyhydric phenol which are bonded more than one aromatic group. Also suitable are polypropylene oxide diepoxide resins, such as DER-732 commercially available from Palmer Holland.

[0065] The active hydrogen-containing, cationic salt group-containing filmforming polymer is made cationic and water dispersible by at least partial neutralization with a neutralizing acid. Suitable neutralizing acids include organic and inorganic acids. Suitable organic neutralizing acids include formic acid, acetic acid, methanesulfonic acid, and lactic acid. Suitable inorganic neutralizing acids include sulfamic acid. By "sulfamic acid" is meant sulfamic acid itself or derivatives thereof such as those having the formula:wherein R is hydrogen or an alkyl group having 1 to 4 carbon atoms. Mixtures of the above-mentioned acids also may be used in the present invention.

[0066] The extent of neutralization of the cationic salt group-containing filmforming polymer may vary with the particular polymer involved. However, sufficient neutralizing acid should be used to sufficiently neutralize the cationic salt group- containing film-forming polymer such that the cationic salt group-containing filmforming polymer may be dispersed in an aqueous dispersing medium. For example,the amount of neutralizing acid used may provide at least 20% of all of the total theoretical neutralization. Excess neutralizing acid may also be used beyond the amount required for 100% total theoretical neutralization. For example, the amount of neutralizing acid used to neutralize the active hydrogen-containing, cationic salt group-containing film-forming polymer may be ^100% based on the total amines in the active hydrogen-containing, cationic salt group-containing film-forming polymer. The total amount of neutralizing acid used to neutralize the cationic salt group- containing film-forming polymer may range between any combination of values, which were recited in the preceding sentences, inclusive of the recited values. For example, the total amount of neutralizing acid used to neutralize the active hydrogen-containing, cationic salt group-containing film-forming polymer may be 20%, 35%, 50%, 60%, or 80% based on the total amines in the cationic salt group- containing film-forming polymer.

[0067] According to the present disclosure, the cationic salt group-containing film-forming polymer may be present in the cationic electrodepositable coating composition in an amount as low as 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, or as high as 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, 85 wt.%, 90 wt.%, 95 wt.%, or within any range encompassed by any two of the foregoing values based on the total weight of the electrocoat composition. For example, the cationic salt group-containing film-forming polymer may be present in an amount of from 5 wt.% to 95 wt.%, 10 wt.% to 90 wt.%, 20 wt.% to 80 wt.%, 30 wt.% to 70 wt.%, or 40 wt.% to 60 wt.%.

[0068] According to the present disclosure, the cationic electrodepositable binder of the cationic electrodepositable coating composition of the present invention may optionally further comprise a curing agent. The curing agent is reactive with functional groups on the film-forming polymer. For example, the curing agent may react with the reactive groups, such as active hydrogen groups, of the cationic salt group-containing film-forming polymer to effectuate cure of the coating composition to form a coating. As used herein, the term “cure”, “cured” or similar terms, as used in connection with the cationic electrodepositable coating compositions described herein, means that at least a portion of the components that form the cationic electrodepositable coating composition are crosslinked to form a coating. Additionally, curing of the cationic electrodepositable coating composition refers tosubjecting said composition to curing conditions (e.g., elevated temperature) leading to the reaction of the reactive functional groups of the components of the cationic electrodepositable coating composition, and resulting in the crosslinking of the components of the composition and formation of an at least partially cured coating. Suitable curing agents are at least partially blocked polyisocyanates, aminoplast resins and phenoplast resins, such as phenolformaldehyde condensates including allyl ether derivatives thereof.

[0069] Suitable at least partially blocked polyisocyanates include aliphatic polyisocyanates, aromatic polyisocyanates, and mixtures thereof. The curing agent may comprise an at least partially blocked aliphatic polyisocyanate. Suitable at least partially blocked aliphatic polyisocyanates include, for example, fully blocked aliphatic polyisocyanates, or partially blocked aliphatic polyisocyanates that are reacted with the polymer backbone. By “blocked” is meant that the isocyanate groups have been reacted with a compound such that the resultant blocked isocyanate group is stable to active hydrogens at ambient temperature but reactive with active hydrogens in the film forming polymer at elevated temperatures, such as between 90°C and 200°C. The polyisocyanate curing agent may be a fully blocked polyisocyanate with substantially no free isocyanate groups.

[0070] The polyisocyanate curing agent may comprise a diisocyanate, higher functional polyisocyanates or combinations thereof. For example, the polyisocyanate curing agent may comprise aliphatic and / or aromatic polyisocyanates. Aliphatic polyisocyanates may include (i) alkylene isocyanates, such as trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (“HDI”), 1 ,2-propylene diisocyanate, 1 ,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1 ,3-butylene diisocyanate, ethylidene diisocyanate, and butylidene diisocyanate, and (ii) cycloalkylene isocyanates, such as 1 ,3-cyclopentane diisocyanate, 1 ,4-cyclohexane diisocyanate, 1 ,2-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexylisocyanate) (“HMDI”), the cyclo-trimer of 1 ,6-hexmethylene diisocyanate (also known as the isocyanurate trimer of HDI, commercially available as Desmodur N3300 from Convestro AG), and meta-tetramethylxylylene diisocyanate (commercially available as TMXDI® from Allnex SA). Aromatic polyisocyanates may include (i) arylene isocyanates, such as m-phenylene diisocyanate, p-phenylene diisocyanate, 1 ,5-naphthalene diisocyanate and 1 ,4-naphthalene diisocyanate, and (ii) alkarylene isocyanates, such as 4,4'-diphenylene methane (“MDI”), 2,4-tolylene or 2,6-tolylene diisocyanate (“TDI”), or mixtures thereof, 4,4-toluidine diisocyanate and xylylene diisocyanate. Triisocyanates, such as triphenyl methane-4,4',4"-triisocyanate, 1 ,3,5- triisocyanato benzene and 2,4,6-triisocyanato toluene, tetraisocyanates, such as 4,4'-diphenyldimethyl methane-2,2’,5,5'-tetraisocyanate, and polymerized polyisocyanates, such as tolylene diisocyanate dimers and trimers and the like, may also be used. The curing agent may comprise a blocked polyisocyanate selected from a polymeric polyisocyanate, such as polymeric HDI, polymeric MDI, polymeric isophorone diisocyanate, and the like. The curing agent may also comprise a blocked trimer of hexamethylene diisocyanate available as Desmodur N3300® from Covestro AG. Mixtures of polyisocyanate curing agents may also be used.

[0071] The polyisocyanate curing agent may be at least partially blocked with at least one blocking agent selected from a 1 ,2-alkane diol, for example 1 ,2- propanediol; a 1 ,3-alkane diol, for example 1 ,3-butanediol; a benzylic alcohol, for example, benzyl alcohol; an allylic alcohol, for example, allyl alcohol; caprolactam; a dialkylamine, for example dibutylamine; and mixtures thereof. The polyisocyanate curing agent may be at least partially blocked with at least one 1 ,2-alkane diol having three or more carbon atoms, for example 1 ,2-butanediol.

[0072] Other suitable blocking agents include aliphatic, cycloaliphatic, or aromatic alkyl monoalcohols or phenolic compounds, including, for example, lower aliphatic alcohols, such as methanol, ethanol, and n-butanol; cycloaliphatic alcohols, such as cyclohexanol; aromatic-alkyl alcohols, such as phenyl carbinol and methylphenyl carbinol; and phenolic compounds, such as phenol itself and substituted phenols wherein the substituents do not affect coating operations, such as cresol and nitrophenol. Glycol ethers and glycol amines may also be used as blocking agents. Suitable glycol ethers include ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether and propylene glycol methyl ether. Other suitable blocking agents include oximes, such as methyl ethyl ketoxime, acetone oxime and cyclohexanone oxime.

[0073] For example, the blocking agent may comprise an ether or polyether comprising a hydroxyl group and a terminal group having the structure -O-R, whereinR is a Ci to C4 alkyl group, such as a Ci to C3 alkyl group. Such blocking groups may comprise the structure:wherein R1 is hydrogen or a methyl group, R2 is a Ci to C4 alkyl group, such as a Ci to C3 alkyl group; and n is an integer from 1-6.

[0074] The curing agent may optionally comprise a high molecular weight volatile group. As used herein, the term “high molecular weight volatile group” refers to blocking agents and other organic byproducts that are produced and volatilized during the curing reaction of the electrodepositable coating composition having a molecular weight of at least 70 g / mol, such as at least 125 g / mol, such as at least 160 g / mol, such as at least 195 g / mol, such as at least 400 g / mol, such as at least 700 g / mol, such as at least 1000 g / mol, or higher, and may range from 70 to 1 ,000 g / mol, such as 160 to 1 ,000 g / mol, such as 195 to 1 ,000 g / mol, such as 400 to 1 ,000 g / mol, such as 700 to 1 ,000 g / mol. For example, the organic byproducts may include alcoholic byproducts resulting from the reaction of the film-forming polymer and an aminoplast or phenoplast curing agent, and the blocking agents may include organic compounds, including alcohols, used to block isocyanato groups of polyisocyanates that are unblocked during cure. For clarity, the high molecular weight volatile groups are covalently bound to the curing agent prior to cure, and explicitly exclude any organic solvents that may be present in the electrodepositable coating composition. Upon curing, the pigment-to-binder ratio of the deposited film may increase in the cured film relative to deposited uncured pigment to binder ratio in the electrodepositable coating composition because of the loss of a higher mass of the blocking agents and other organic byproducts derived from the curing agent that are volatilized during cure. High molecular weight volatile groups may comprise 5% to 50% by weight of the film-forming binder, such as 7% to 45% by weight, such as 9% to 40% by weight, such as 11% to 35%, such as 13% to 30%, based on the total weight of the film-forming binder. The high molecular weight volatile groups and other lower molecular weight volatile organic compounds produced during cure, such as lower molecular weight blocking agents and organic byproducts produced duringcure, may be present in an amount such that the relative weight loss of the filmforming binder deposited onto the substrate relative to the weight of the film-forming binder after cure is an amount of 5% to 50% by weight of the film-forming binder, such as 7% to 45% by weight, such as 9% to 40% by weight, such as 11 % to 35%, such as 13% to 30%, based on the total weight of the film-forming binder before and after cure.

[0075] The curing agent may comprise an aminoplast resin. Aminoplast resins are condensation products of an aldehyde with an amino- or amido-group carrying substance. Condensation products obtained from the reaction of alcohols and an aldehyde with melamine, urea or benzoguanamine may be used. However, condensation products of other amines and amides may also be employed, for example, aldehyde condensates of triazines, diazines, triazoles, guanidines, guanamines and alkyl- and aryl-substituted derivatives of such compounds, including alkyl- and aryl-substituted ureas and alkyl- and aryl-substituted melamines. Suitable compounds are N,N'-dimethyl urea, benzourea, dicyandiamide, formaguanamine, acetoguanamine, ammeline, 2-chloro-4,6-diamino-1 ,3,5-triazine, 6-methyl-2,4- diamino-1 ,3,5-triazine, 3,5-diaminotriazole, triaminopyrimidine, 2-mercapto-4,6- diaminopyrimidine, 3, 4, 6-tris(ethylamino)-1 ,3,5-triazine, and the like. Suitable aldehydes include formaldehyde, acetaldehyde, crotonaldehyde, acrolein, benzaldehyde, furfural, glyoxal and the like.

[0076] The aminoplast resins may contain methylol or similar alkylol groups, and at least a portion of these alkylol groups may be etherified by a reaction with an alcohol to provide organic solvent-soluble resins. Any monohydric alcohol may be employed for this purpose, including such alcohols as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol and others, as well as benzyl alcohol and other aromatic alcohols, cyclic alcohol such as cyclohexanol, monoethers of glycols such as Cello solves and Carbitols, and halogen-substituted or other substituted alcohols, such as 3-chloropropanol and butoxyethanol.

[0077] Suitable commercially available aminoplast resins are those available under the trademark CYMEL® from Allnex Belgium SA / NV, such as CYMEL 1 130 and 1156, and RESIMENE® from INEOS Melamines, such as RESIMENE 750 and 753. Suitable aminoplast resins 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 being herebyincorporated by reference. As is disclosed in the aforementioned portion of the '679 patent, the aminoplast may be used in combination with the methylol phenol ethers.

[0078] Phenoplast resins are formed by the condensation of an aldehyde and a phenol. Suitable aldehydes include formaldehyde and acetaldehyde. Methylene- releasing and aldehyde-releasing agents, such as paraformaldehyde and hexamethylene tetramine, may also be utilized as the aldehyde agent. Various phenols may be used, such as phenol itself, a cresol, or a substituted phenol in which a hydrocarbon radical having either a straight chain, a branched chain or a cyclic structure is substituted for a hydrogen in the aromatic ring. Mixtures of phenols may also be employed. Some specific suitable phenols are p-phenylphenol, p-tert- butylphenol, p-tert-amylphenol, cyclopentylphenol and unsaturated hydrocarbonsubstituted phenols, such as the monobutenyl phenols containing a butenyl group in ortho, meta or para position, and where the double bond occurs in various positions in the hydrocarbon chain.

[0079] Aminoplast and phenoplast resins, as described above, 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 being incorporated herein by reference.

[0080] The curing agent may be present in the cationic electrodepositable coating composition in an amount as low as 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, 40 wt.%, 45 wt.%, 50 wt.%, or as high as 55 wt.%, 60 wt.%, 65 wt.%, 70 wt.%, 75 wt.%, 80 wt.%, 85 wt.%, 90 wt.%, 95 wt.%, or within any range encompassed by any two of the foregoing values based on the total weight of the electrocoat composition. For example the curing agent may be present in an amount of from 5 wt.% to 95 wt.%, 10 wt.% to 90 wt.%, 20 wt.% to 80 wt.%, 30 wt.% to 70 wt.%, or 40 wt.% to 60 wt.%.

[0081] The e-coat compositions may also include an additive comprising oxazolidone groups. For example, the additive may comprise at least two oxazolidone functionalities. The chemical structure of the additive may also connective groups which are chemically bonded to an oxazolidone functionality and to a terminal group. The connective groups may be aromatic functional groups and / or aliphatic functional groups. The terminal groups may be at each end of the oxazolidone functional additive and bound to the connective groups. The terminalgroups may comprise an amine group. The entire oxazolidone additive structure may also be free from epoxy groups.

[0082] Structures of the oxazolidone additive are shown in Table 1 below:Table 1E-Coat Oxazolidone Structures

[0083] The coating composition comprising the oxazolidone additive may have an oxazolidone group equivalent per coating weight of as low as 100 g / equivalent wt., 200 g / equivalent wt., 300 g / equivalent wt., 400 g / equivalent wt., 500 g / equivalent wt., 600 g / equivalent wt., 700 g / equivalent wt., 800 g / equivalent wt., 900 g / equivalent wt., or as high as 1 ,000 g / equivalent wt., 1 ,100 g / equivalent wt., 1 ,200 g / equivalent wt., 1 ,300 g / equivalent wt., 1 ,400 g / equivalent wt., 1 ,500 g / equivalent wt., 1 ,600 g / equivalent wt., 1 ,700 g / equivalent wt., 1 ,800 g / equivalent wt., 1 ,900 g / equivalent wt., 2,000 g / equivalent wt., or within any range encompassed by any of the foregoing values as endpoints. For example, the oxazolidone group equivalent per coating weight may be from 100 g / equivalent wt. to 1 ,500 g / equivalent wt., from 200 g / equivalent wt. to 1 ,000 g / equivalent wt., or from 300 g / equivalent wt. to 700 g / equivalent wt.

[0084] The oxazolidone additive may be present in the E-coat compositions in an amount as low as 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, or as high as 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%, 20 wt.%, or within any range encompassed byany two of the foregoing values as endpoints. For example, the oxazolidone additive may be present in an amount of from 1 wt.% to 13 wt.%, 2 wt.% to 12 wt.%, 3 wt.% to 11 wt.%, or 4 wt.% to 10 wt.%, based on the total weight of the E-coat compositions..

[0085] The cationic electrodepositable coating composition of the present invention may be applied onto a number of substrates. Accordingly, the present invention is further directed to a substrate that is coated, at least in part, with a coating deposited from the cationic electrodepositable coating composition described herein. It will be understood that the cationic electrodepositable coating composition can be applied onto a substrate as a monocoat or as a coating layer in a multi-layer coating composite. The cationic electrodepositable coating composition may be electrophoretically deposited upon any electrically conductive substrate. Suitable substrates 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. According to the present invention, the metal or metal alloy may comprise cold rolled steel, hot rolled steel, steel coated with zinc metal, zinc compounds, or zinc alloys, such as electrogalvanized steel, hot-dipped galvanized steel, galvannealed steel, and steel plated with zinc alloy. Aluminum alloys of the 2XXX, 5XXX, 6XXX, or 7XXX series as well as clad aluminum alloys and cast aluminum alloys of the A356 series also may be used as the substrate. Magnesium alloys of the AZ31 B, AZ91C, AM60B, or EV31 A series also may be used as the substrate. The substrate used in the present invention may also comprise titanium and / or titanium alloys. Other suitable nonferrous metals include copper and magnesium, as well as alloys of these materials. Suitable metal substrates for use in the present invention 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, agricultural equipment, lawn and garden equipment, air conditioning units, heat pump units, lawn furniture, and other articles. As used herein, “vehicle” or variationsthereof includes, but is not limited to, civilian, commercial and military aircraft, and / or land vehicles such as cars, motorcycles, and / or trucks. The metal substrate also may be in the form of, for example, a sheet of metal or a fabricated part. It will also be understood that the substrate may be pretreated with a pretreatment solution including a zinc phosphate pretreatment solution such as, for example, those described in U.S. Pat. Nos. 4,793,867 and 5,588,989, or a zirconium containing pretreatment solution.

[0086] The coating composition may be applied as a single layer to an uncoated substrate. For example, the coating composition can be applied to the substrate to form a monocoat. As used herein, a "monocoat" refers to a single coating layer that is free of additional coating layers. Thus, the coating composition can be applied directly to a substrate and cured to form a single layer coating, i.e., a monocoat.

[0087] The coated substrate of the present disclosure may further comprise one or more additional coating layers, such as a second overcoat deposited onto at least a portion of the first coating composition, to form a multi-layer coating such as by applying a topcoat. When a multi-layer coating is formed, the first coating composition can be cured prior to application of additional overcoats, or one or more of the additional overcoats and the first coating composition can be cured simultaneously. It is appreciated that the second overcoat and additional overcoat can be in solid or liquid form. The coating compositions may be layered underneath a topcoat or series of topcoats to form a stackup. The coating composition may be a first layer applied to a bare substrate as an undercoating or primer. The primer may then have subsequent layers applied on top of it to form a multi-layer coating.

[0088] The electrocoated articles contemplated by the present disclosure may have a low scribe creep as measured according to ASTM B117-19. For example, the coated articles may have a scribe creep of less than 20%, less than 19%, less than 18%, less than 17%, less than 16%, less than 15%, less than 14%, less than 13%, less than 12%, less than 11 %, less than 10%, less than 9%, less than 8%, less than 7%, less than 6%, less than 5%, less than 4%, less than 3%, less than 2%, or less than 1 %.

[0089] The electrocoated articles contemplated by the present disclosure may also have a high score on the crosshatch adhesion test as measured according toASTM D3359-22. The coating may demonstrate a ranking of 0B or higher, 1 B or higher, 2B or higher, 3B or higher, 4B or higher, or 5B.IV. Powder Coating Compositions

[0090] Powder coatings are solvent-free or reduced solvent coating systems used in a number of applications, including automotive coatings, household appliances, architectural and construction components, furniture, agricultural machinery, and electronics. Powder coatings are made of a thermosetting resin system and are typically applied to a substrate electrostatically and cured at elevated temperatures (e.g., at or above 300 °F).

[0091] The present disclosure provides a powder coating composition comprising a film forming resin and an additive comprising oxazolidone functionalities. The powder coating composition may also include an optional curing agent.

[0092] The powder coating compositions in accordance with the present disclosure can include any of a variety of thermosetting powder coating compositions known in the art. As used herein, the term “thermosetting” refers to compositions that “set” irreversibly upon curing or crosslinking, wherein polymer chains of polymeric components are joined together by covalent bonds. This property is usually associated with a cross-linking reaction of the composition constituents often induced, for example, by heat or radiation. Once cured, a thermosetting resin will not melt upon the application of heat and is insoluble in solvents.

[0093] The powder coating compositions used with the present invention can also include thermoplastic powder coating compositions. As used herein, the term “thermoplastic” refers to compositions that include polymeric components that are not joined by covalent bonds and, thereby, can undergo liquid flow upon heating and are soluble in solvents.

[0094] Suitable film-forming resins that form at least a portion of the binder of the powder coating composition include (meth)acrylate resins, polyurethanes, polyesters, polyamides, polyethers, polysiloxanes, epoxy resins, vinyl resins, copolymers thereof, and combinations thereof. As used herein, “(meth)acrylate” and like terms refers both to the acrylate and the corresponding methacrylate. Further, the film-forming resins can have any of a variety of functional groups including, butnot limited to, carboxylic acid groups, amine groups, epoxide groups, hydroxyl groups, thiol groups, carbamate groups, amide groups, urea groups, isocyanate groups (including blocked isocyanate groups), and combinations thereof.

[0095] Thermosetting coating compositions typically comprise a crosslinker that may be selected from any of the crosslinkers known in the art to react with the functionality of one or more film-forming resins used in the powder coating composition. As used herein, the term “crosslinker” refers to a molecule comprising two or more functional groups that are reactive with other functional groups and that is capable of linking two or more monomers or polymers through chemical bonds. Alternatively, the film-forming resins that form the binder of the powder coating composition can have functional groups that are reactive with themselves; in this manner, such resins are self-crosslinking.

[0096] Suitable crosslinkers include phenolic resins, amino resins, epoxy resins, beta-hydroxy (alkyl) amides, alkylated carbamates, (meth)acrylates, isocyanates, blocked isocyanates, polyacids, anhydrides, organometallic acidfunctional materials, polyamines, polyamides, aminoplasts, carbodiimides, oxazolines, and combinations thereof.

[0097] The powder coating compositions can also be substantially free, essentially free, or completely free of any of the previously described film-forming resins and / or crosslinkers. For example, the powder coating composition can be substantially free, essentially free, or completely free of a hydroxyl functional filmforming resin and / or an isocyanate functional crosslinker. The term “substantially free” as used in this context means the powder coating composition contains less than 1000 parts per million (ppm), “essentially free” means less than 100 ppm, and “completely free” means less than 20 parts per billion (ppb) of a hydroxyl functional film-forming resin and / or an isocyanate functional crosslinker, based on the total weight of the powder coating composition.

[0098] The powder coating composition can also include other optional materials. For example, the powder coating compositions can also comprise a colorant. As used herein, “colorant” refers to any substance that imparts color and / or other opacity and / or other visual effect to the composition. The colorant can be added to the coating in any suitable form, such as discrete particles, dispersions,solutions, and / or flakes. A single colorant or a mixture of two or more colorants can be used in the coatings of the present invention.

[0099] Colorants include pigments (organic or inorganic), dyes and tints, such as those used in the paint industry and / or listed in the Dry Color Manufacturers Association (DCMA), as well as special effect compositions. A colorant may include, for example, a finely divided solid powder that is insoluble, but wettable, under the conditions of use. A colorant can be organic or inorganic and can be agglomerated or non-agglomerated. Colorants can be incorporated into the coatings by use of a grind vehicle, such as an acrylic grind vehicle, the use of which will be familiar to one skilled in the art.

[0100] Pigments and / or pigment compositions include, but are not limited to, carbazole dioxazine crude pigment, azo, monoazo, diazo, naphthol AS, benzimidazolone, isoindolinone, isoindoline and polycyclic phthalocyanine, quinacridone, perylene, perinone, diketopyrrolo pyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone, dioxazine, triarylcarbonium, quinophthalone pigments, diketo pyrrolo pyrrole red (“DPPBO red”), titanium dioxide, carbon black, and mixtures thereof. The terms “pigment” and “colored filler” can be used interchangeably.

[0101] Dyes include, but are not limited to, those that are solvent and / or aqueous based such as phthalo green or blue, iron oxide, bismuth vanadate, anthraquinone, and perylene and quinacridone.

[0102] Tints include, but are not limited to, pigments dispersed in water-based or water miscible carriers such as AQUA-CHEM 896 commercially available from Degussa, Inc., CHARISMA COLORANTS and MAXITONER INDUSTRIAL COLORANTS commercially available from Accurate Dispersions Division of Eastman Chemical, Inc.

[0103] Other suitable materials that can be used with the powder coating compositions of the present invention include plasticizers, abrasion resistant particles, fillers including, but not limited to, micas, talc, clays, and inorganic minerals, metal oxides, metal flake, various forms of carbon, anti-oxidants, hindered amine light stabilizers, UV light absorbers and stabilizers, surfactants, flow and surface control agents, thixotropic agents, catalysts, reaction inhibitors, corrosioninhibitors, and other customary auxiliaries.

[0104] The powder coating compositions may also include an additive comprising oxazolidone groups. For example, the oxazolidone additive may comprise at least two oxazolidone functionalities. The chemical structure of the additive may also have a linking group which separates the two oxazolidone functionalities. The linking group may be an aromatic group. The additive may also comprise two connective groups which are chemically bonded to the oxazolidone functionalities and to terminal groups. The connective groups may comprise an aromatic group or an aliphatic group. For example, the connective groups may comprise bisphenol A. The terminal group may comprise an epoxy group. Structures of the oxazolidone additive are shown in Table 2 below:Table 2Powder Coating Oxazolidone Structures

[0105] The oxazolidone additive may be present in the coating composition in an amount as low as 0.1 wt.%, 0.5 wt.%, 1 wt.%, 5 wt.%, 10 wt.%, 15 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.%, or as high as 40 wt.%, 45 wt.%, 50 wt.%, 55 wt.%, 60 wt.% or within any range encompassed by any two of the foregoing values as endpoints, based on the total weight of the coating composition. For example, the oxazolidone additive may be present in an amount of from 0.1 wt.% to 40 wt.%, from 0.5 wt.% to 40 wt.%, from 1 wt.% to 40 wt.%, from 1 wt.% to 30 wt.%, from 5 wt.% to 25 wt.%, or from 10 wt.%, to 20 wt.%.

[0106] The powder coating composition of the present invention may be applied onto a number of substrates. Accordingly, the present disclosure is further directed to a substrate that is coated, at least in part, with a coating deposited from the powder coating composition described herein. It will be understood that the powder coating composition can be applied onto a substrate as a monocoat or as a coating layer in a multi-layer coating composite.

[0107] The components of the powder coating compositions may be contacted through mixing, grinding, or any suitable contacting method. The components may be a solid at room temperature (23°C) and more specifically may be a powder withan average particle size. The individual components may be contacted in any suitable ratio to form the coating composition.

[0108] The substrate may be preheated to a surface temperature or a bulk temperature before the application of the coating composition. The substrate may be heated to a surface temperature of as little as 100 °F, 125 °F, 150 °F, 175 °F, 200 °F, or as great as 225 °F, 250 °F, 275 °F, 300 °F, 325 °F, 350 °F, 375 °F, 400 °F, or any range including any two of these values as endpoints. Stated differently, the substrate may be heated to a surface temperature of as little as 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, or as great as 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C or any range including any two of these values as endpoints. The substrate may be heated to a surface temperature from 40°C to 150°C, from 50°C to 150°C, from 60°C to 150°C, from 70°C to 150°C, from 80°C to 150°C, from 90°C to 150°C, from 100°C to 150°C, from 110°C to 150°C, from 110°C to 140°C, or from 120°C to 140°C.

[0109] Once the coating composition has been applied to the substrate, the coating is cured. The curable coating composition may be cured with heat, increased or reduced pressure, chemically such as with moisture, or with other means such as actinic radiation, and combinations thereof. Curing may comprise an initial curing step with radiation, followed by heating. The term “actinic radiation” refers to electromagnetic radiation that can initiate chemical reactions. Actinic radiation includes, but is not limited to, visible light, ultraviolet (UV) light, infrared (I R), X-ray, and gamma radiation.

[0110] The coating composition may be cured at a low temperature. The coating composition may be cured at less than 450 °F, less than 425 °F, less than 400 °F, less than 375 °F, less than 350 °F, less than 325 °F, less than 300 °F, less than 290 °F, less than 280 °F, less than 275 °F, less than 270 °F, less than 260 °F, less than 250 °F, or any range including any two of these values as endpoints. Stated differently, the coating composition may be cured at less than 240°C, less than 230°C, less than 220°C, less than 210°C, less than 200°C, less than 190°C, less than 180°C, less than 170°C, less than 160°C, less than 150°C, less than 140°C, less than 130°C, less than 120°C, or any range including any two of these values as endpoints. The coating composition may be cured at a temperature from 120°C to 200°C, from 120°C to 190°C, from 120°C to 180°C, from 120°C to 170°C,from 120°C to 160°C, from 120°C to 150°C, from 120°C to 140°C, or from 120°C to 130°C.

[0111] The curing step may be carried out for any suitable time to allow the coating to fully or at least partially cure. The curing time may vary depending on the substrate, the coating composition, the coating thickness, ambient conditions, curing methods, or any combination of these factors. Curing time may be as little as 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, or as great as 60 minutes, 55 minutes, 50 minutes, 45 minutes, 40 minutes, 35 minutes, 30 minutes, 25 minutes, 20 minutes, 15 minutes, 12 minutes, or any range including any two of these values as endpoints. The curing time may be from 1 minute to 30 minutes, from 1 minute to 20 minutes, from 1 minute to 15 minutes, from 1 minute to 10 minutes, from 1 minute to 6 minutes, from 5 minutes to 15 minutes, from 5 minutes to 10 minutes, or from 3 minutes to 9 minutes.

[0112] The overall coating on the substrate may have a thickness of as little as 0.1 mils, 0.2 mils, 0.3 mils, 0.4 mils, 0.5 mils, 0.6 mils, 0.7 mils, 0.8 mils, 0.9 mils, 1 mil, 1 .5 mils, 2 mils, 2.5 mils or as great as 20 mils, 15 mils, 14 mils, 13 mils, 12 mils, 11 mils, 10 mils, 9 mils, 8 mils, 7 mils, 6 mils, 5 mils, 4 mils, 3.9 mils, 3.8 mils, 3.7 mils, 3.6 mils, 3.5 mils, 3.4 mils, 3.3 mils, 3.2 mils, 3.1 mils, 3 mils, or any range including any two of these amounts as endpoints. The overall coating may have a thickness of 1 mils to 4 mils, 1 .5 mils to 2.5 mils, or 2 mils to 3 mils. The thickness may be measured according to the ASTM D7091-13 test method using and Elcometer 415 Model B Dual FNF film gauge.

[0113] Other application methods that can be used to apply the coating composition onto the substrate include: spraying, such as by incorporating the coating composition into a liquid formulation and using spray equipment; wiping where the coating composition is contained on and / or in a wipe and manually or automatically wiped; media blasting where the coating composition is a solid and is blasted onto the substrate's surface; electrostatically applied as a powder; brushing or rolling the coating composition over the substrate such as by incorporating the coating composition into a formulation ( e.g., liquid or gel) that can be brushed or rolled; vapor deposition; electrodeposition where the formulation is liquid and is electro-coated; or any combination thereof. The coating composition may also beapplied in-mold, during extrusion, during a calendaring, or during other processing of substrate materials.

[0114] The coating composition may be applied directly to a substrate without any intermediate layers between the coating composition and the substrate. The coating composition may be applied directly to a metal substrate, before or after the substrate is cleaned and / or treated as further described herein, but before application of any coating layers. The coating composition may also be applied during cleaning such as a component of the cleaner. The coating composition may be applied over the entire surface, edges, and corners of the substrate, or the coating composition may be applied over selected portions of the substrate.

[0115] The coating composition may also form a continuous or semi- continuous layer over the substrate, or the coating composition may be applied over certain spots / areas of the substrate such as the edges and comers of the substrate. As used herein, the area referred to as the "edge" will vary based on the particular substrate but may include, e.g., the outer most lateral face of the substrate.

[0116] The coating composition may be applied as a single layer to an uncoated substrate. For example, the coating composition can be applied to the substrate to form a monocoat. As used herein, a "monocoat" refers to a single coating layer that is free of additional coating layers. Thus, the coating composition can be applied directly to a substrate and cured to form a single layer coating, i.e., a monocoat.

[0117] The coated substrate of the present disclosure may further comprise one or more additional coating layers, such as a second overcoat deposited onto at least a portion of the first coating composition, to form a multi-layer coating such as by applying a topcoat. When a multi-layer coating is formed, the first coating composition can be cured prior to application of additional overcoats, or one or more of the additional overcoats and the first coating composition can be cured simultaneously. It is appreciated that the second overcoat and additional overcoat can be in solid or liquid form. The coating compositions may be layered underneath a topcoat or series of topcoats to form a stackup. The coating composition may be a first layer applied to a bare substrate as an undercoating or primer. The primer may then have subsequent layers applied on top of it to form a multi-layer coating.

[0118] The powder coated articles contemplated by the present disclosure may have a low scribe creep as measured according to ASTM B117-19. For example, the coated articles may have a scribe creep of less than 60%, less than 55%, less than 50%, less than 45%, less than 40%, less than 35%, less than 30%, less than 25%, less than 20%, less than 19%, less than 18%, less than 17%, less than 16%, less than 15%, less than 14%, less than 13%, less than 12%, less than 11 %, less than 10%, less than 9%, less than 8%, less than 7%, less than 6%, less than 5%, less than 4%, less than 3%, less than 2%, or less than 1 %, or within any range encompassed by any two of the foregoing values as endpoints. For example, the powder coated articles may have a scribe creep of from 1% to 60%, from 10% to 50%, or from 20% to 40%.

[0119] The powder coated articles may also have a scribe creep measured according to ASTM B117-19 of as low as 40 mm or less, 39 mm or less, 38 mm or less, 37 mm or less, 36 mm or less, 35 mm or less, 34 mm or less, 33 mm or less, 32 mm or less, 31 mm or less, 30 mm or less, 29 mm or less, 28 mm or less, 27 mm or less, 26 mm or less, 25 mm or less, 24 mm or less, 23 mm or less, 22 mm or less, 21 mm or less, 20 mm or less, 19 mm or less, 18 mm or less, 17 mm or less, 16 mm or less, 15 mm or less, 14 mm or less, 13 mm or less, 12 mm or less, 11 mm or less, 10 mm or less, 9 mm or less, 8 mm or less, 7 mm or less, 6 mm or less, 5 mm or less, 4 mm or less, 3 mm or less, 2 mm or less, 1 mm or less, or within any range encompassed by any two of the foregoing values as endpoints. For example, the powder coated articles may have a scribe creep of from 1 mm to 10 mm.

[0120] The coating once cured on top of an article may be thermally conductive. For example, the coating may have a thermal conductivity of at least 0.3 W / m K, as measured according to ASTM D7984, such as at least 0.5 W / m K, such as at least 0.7 W / m K, such as at least 0.9 W / m K, such as at least 1 .5 W / m K, or higher.

[0121] The powder coated articles contemplated by the present disclosure may show little change in gloss or color when exposed to UV light. They may be tested for UV light resistance according to SAE J2527 or SAE J2020 UVA for accelerated weathering exposure to simulate outdoor exposure to sunlight on an accelerated basis.V. Liquid Coating Compositions

[0122] Liquid polymer coating compositions are routinely applied to substrates, especially metal substrates to protect the substrate from degradation, to beautify the substrate (e.g., to provide color, brightness, etc.), and / or to reflect light. Many such polymer coating compositions are applied on planar substrate (e.g., using coil coating processes) which is subsequently formed into a finished article.

[0123] The present disclosure provides liquid coating compositions comprising a polyester resin and an additive comprising oxazolidone functionalities. The liquid coating composition may also comprise an optional curing agent.

[0124] Polyesters that may be utilized as the resin in the present disclosure and methods of preparing them are well known in the art. The polyesters may be prepared from polybasic carboxylic acids or their esterifiable derivatives and from polyols by any suitable known process. With regard to the polyols which can be used when practicing this invention, they can include any material that contains a reactive hydrogen atom and that would react with the isocyanate or isocyanurate group. These materials include hydroxyl functional acrylics, hydroxyl functional polyesters, hydroxy functional polyethers, polyamines, polyamides, short oil alkyds, caster oil, epoxy resins with secondary hydroxyl groups, phenolic resins, and hydroxyl functional vinyl resins. If necessary, the vinyl resins may be used to promote adhesion.

[0125] Suitable polyhydric alcohols include ethylene glycol, propylene glycol, butylene glycol, 1 ,6-hexylene glycol, neopentyl glycol, diethylene glycol, glycerol, trimethylol propane and pentaerythritol. The polycarboxylic acids may include succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and trimellitic acid.

[0126] To aid in the crosslinking of the film forming resin, the liquid coating compositions in accordance with the present disclosure may also comprise a crosslinking agent. The cross linking agent may, for example, be an isocyanate crosslinking agent.

[0127] With regard to the isocyanates which can be used, they can be divided into four different categories. The four types include diphenylmethane 4,4'-diisocyanate (MDI), toluene diisocyanate (TDI), isophorone diisocyanate (I PDI), and hexamethylene diisocyanate (HDI).

[0128] Polyisocyanates based on HDI represent a significant category of polyisocyanates used in polyurethane coatings. Specifically, those coatings which are prepared using HDI-based products typically show additional resistance to chemicals and abrasion. They also tend to exhibit desirable weathering characteristics, including retention of gloss, and resistance to yellowing and chalking.

[0129] BAYER's Desmodur N-75, Desmodur N-100, and Desmodur N-3200 are suitable commercially known polyisocyanates which are based on HDI. They are polymeric materials which contain biuret groups. The HDI may be converted into a trimer containing an isocyanurate ring. Such product are commercially available from BAYER under the product names Desmodur N-3300 and Desmodur N-3390.

[0130] The liquid coating compositions may also comprise any suitable solvent. Suitable solvents include aromatic hydrocarbons, for example, toluene, xylene and ketones, such as, methyl ethyl ketone and methyl isobutyl ketone, methyl isoamyl ketone (MIAK), methylamyl ketone (MAK), methylether propylene glycol acetate, and the like, and combinations thereof.

[0131] The liquid coating compositions may also comprise a pigment or colorant to change the visual appearance of the coating. Colorants can be organic or inorganic dyes and tints, such as those used in the paint industry and / or listed in the Dry Color Manufacturers Association (DCMA), as well as special effect compositions. A colorant may include a finely divided solid powder that is insoluble, but wettable, under the conditions of use. A colorant may be organic or inorganic and may be agglomerated or non-agglomerated. Colorants may be incorporated into the coatings by use of a grind vehicle, such as an acrylic grind vehicle, the use of which will be familiar to one skilled in the art. Colorants and / or colorant compositions may include, but are not limited to, carbazole dioxazine crude pigment, azo, monoazo, diazo, naphthol AS, benzimidazolone, isoindolinone, isoindoline and polycyclic phthalocyanine, quinacridone, perylene, perinone, diketopyrrolo pyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone, dioxazine, triarylcarbonium, quinophthalone pigments, diketo pyrrolo pyrrole red ("DPPBO red"), titanium dioxide, carbon black, and mixtures thereof. Colorants may also include, but are not limited to, those that are solvent and / oraqueous based such as phthalo green or blue, iron oxide, bismuth vanadate, anthraquinone, and perylene, and quinacridone.

[0132] The liquid coating compositions may also may further optionally comprise flow control agents, sometimes called leveling agents, which are useful to promote the formation of a continuous and even coating. Suitable flow control agents include polyacrylic esters, non-ionic fluorinated alkyl ester surfactants, non-ionic alkylarylpolyether alcohols, silicones, and the like, and combinations comprising at least two of the foregoing flow control agents. Flow control agents are generally liquids at room temperature that have been converted to powder form by absorption onto silica-type materials. One flow control agent is a 2-propenoic acid, ethyl ester polymer acrylic resin, available under the tradename RESIFLOW® P-67 by Estron Chemical, Inc.; a 2-hydroxy-1 ,2-diphenylethanone crystalline solid that is believed to keep the molten coating open for a suitable time to allow outgassing to occur prior to the formation of the hard-set film, sold under the tradename Benzoin by DSM, Inc. The liquid coating composition may also include a dry flow agent such as fumed silica or colloidal aluminum oxide such as the ones sold under the tradename AEROSIL® by Evonik Corporation.

[0133] The liquid coating compositions may also include an additive comprising oxazolidone groups. For example, the oxazolidone additive may comprise at least two oxazolidone functionalities. The at least two oxazolidone functionalities may both be bonded to a single linking group. The oxazolidone functionalities may also be bonded to at least two connective groups which are bonded to terminal groups. The connective groups may comprise an aromatic group or an aliphatic group and the terminal groups may comprise an epoxy group, an acid group, a hydroxyl group, an amine group, an aromatic group, or an aliphatic group.

[0134] The oxazolidone additive may have a backbone structure which comprises poly-THF.

[0135] Structures of the oxazolidone additive are shown in Table 3 below:Table 3Liquid Coating Oxazolidone Structures

[0136] The oxazolidone additive may be present in the liquid coating compositions in an amount as low as 1 wt.%, 2 wt.%, 3 wt.%, 4 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, or as high as 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%, 20 wt.%, or within any range encompassed by any two of the foregoing values as endpoints. For example, the oxazolidone additive may be present in an amount of from 1 wt.% to 11 wt.%, 2 wt.% to 10 wt.%, 3 wt.% to 9 wt.%, 4 wt.% to 8 wt.%, or 5 wt.% to 7 wt.%.

[0137] The liquid coating composition of the present invention may be applied onto a number of substrates. Accordingly, the present disclosure is further directed to a substrate that is coated, at least in part, with a coating deposited from the liquid coating composition described herein. Suitable substrates include steel and coated steel such as iron phosphate pretreated steel and zirconium pretreated steel.

[0138] The coating composition may be applied as a single layer to an uncoated substrate. For example, the coating composition can be applied to the substrate to form a monocoat. As used herein, a "monocoat" refers to a single coating layer that is free of additional coating layers. Thus, the coating composition can be applied directly to a substrate and cured to form a single layer coating, i.e., a monocoat.

[0139] The coated substrate of the present disclosure may further comprise one or more additional coating layers, such as a second overcoat deposited onto at least a portion of the first coating composition, to form a multi-layer coating such as by applying a topcoat. When a multi-layer coating is formed, the first coatingcomposition can be cured prior to application of additional overcoats, or one or more of the additional overcoats and the first coating composition can be cured simultaneously. It is appreciated that the second overcoat and additional overcoat can be in solid or liquid form. The coating compositions may be layered underneath a topcoat or series of topcoats to form a stackup. The coating composition may be a first layer applied to a bare substrate as an undercoating or primer. The primer may then have subsequent layers applied on top of it to form a multi-layer coating.

[0140] The liquid coated articles contemplated by the present disclosure may have a low scribe creep as measured according to ASTM B117-19. For example, the coated articles may have a scribe creep of less than 20%, less than 19%, less than 18%, less than 17%, less than 16%, less than 15%, less than 14%, less than 13%, less than 12%, less than 11 %, less than 10%, less than 9%, less than 8%, less than 7%, less than 6%, less than 5%, less than 4%, less than 3%, less than 2%, or less than 1 %.

[0141] In addition, the liquid coated articles may have a reduction in scribe creep of at least 10% according to ASTM B117-19 compared to an article coated with the same oxazolidone free coating. For example, the reduction in scribe creep may be at least 11%, at least 12%, at least 13%, at least 14%, at least 15%, at least 16%, at least 17%, at least 18%, at least 19%, or at least 20%.VI. Packaging Coating Compositions

[0142] A wide variety of coatings are used to coat the surfaces of packaging containers. Packaging containers are available in a variety of different configurations in order to accommodate the multitude of different packaging end uses and packaged products. The inner surface of metal packaging containers is typically coated with one or more coatings to avoid unsuitable interactions between the metal substrate and ingredients of the packaged product, which can result in corrosion of the metal substrate and / or adulteration of the packaged product.

[0143] The present disclosure provides a packaging coating composition comprising a polyester resin, acrylic modified polyester, or acrylic resin (latex); and an additive comprising oxazolidone functionalities. The packaging coating composition may also include an optional curing agent.

[0144] The film forming resin of the packaging coating composition may be a polyester resin. Polyesters that may be utilized as the resin in the present disclosure and methods of preparing them are well known in the art. The polyesters may be prepared from polybasic carboxylic acids or their esterifiable derivatives and from polyols by any suitable known process. With regard to the polyols which can be used when practicing this invention, they can include any material that contains a reactive hydrogen atom and that would react with the isocyanate or isocyanurate group, melamine, phenolic, or benzoguanamine. These materials include hydroxyl functional acrylics, hydroxyl functional polyesters, hydroxy functional polyethers, polyamines, polyamides, short oil alkyds, caster oil, epoxy resins with secondary hydroxyl groups, phenolic resins, and hydroxyl functional vinyl resins. If necessary, the vinyl resins may be used to promote adhesion.

[0145] The polyester material may be formed from any suitable polyacid. Suitable polyacids include, but are not limited to the following: maleic acid; fumaric acid; itaconic acid; adipic acid; azelaic acid; succinic acid; sebacic acid; glutaric acid; decanoic diacid; dodecanoic diacid; phthalic acid; isophthalic acid; 5-tert- butylisophthalic acid; tetrachlorophthalic acid; tetrahydrophthalic acid; trimellitic acid; naphthalene dicarboxylic acid; naphthalene tetracarboxylic acid; terephthalic acid; hexahydrophthalic acid; methylhexahydrophthalic acid; dimethyl terephthalate; cyclohexane dicarboxylic acid; chlorendic anhydride; 1 ,3-cyclohexane dicarboxylic acid; 1 ,4-cyclohexane dicarboxylic acid; tricyclodecane polycarboxylic acid; endomethylene tetrahydrophthalic acid; endoethylene hexahydrophthalic acid; cyclohexanetetra carboxylic acid; cyclobutane tetracarboxylic; an acidic monomer having an aliphatic group containing at least 15 carbon atoms; esters and anhydrides of all the aforementioned acids and combinations thereof.

[0146] Suitably, the carboxylic acid groups of the polyacid may be connected by an arylene bridging group. Thus, suitably, the polyacid may comprise an aromatic polyacid.

[0147] The polyacid component may comprise terephthalic acid (TPA), isophthalic acid (IPA), dimethyl terephthalate, dimethyl isophthalic acid, 1 ,4- cyclohexane dicarboxylic acid, hexahydrophthalic anhydride, 2,6-naphthalene dicarboxylic acid, adipic acid, phthalic anhydride, maleic anhydride, and / or fumaric anhydride.

[0148] The polyester material may be formed from a diacid. The polyester material may be formed from any suitable diacid. Suitable diacids include, but are not limited to the following: phthalic acid; isophthalic acid; terephthalic acid; 1 ,4-4- cyclohexane dicarboxylic acid; succinic acid; adipic acid; azelaic acid; sebacic acid; fumaric acid; 2,6-naphthalene dicarboxylic acid; orthophthalic acid; phthalic anhydride; tetrahydrophthalic anhydride; maleic anhydride; succinic anhydride; itaconic anhydride; di-ester materials, such as dimethyl ester derivatives for example dimethyl isophthalate, dimethyl terephthalate, dimethyl 1 ,4-cyclohexane dicarboxylate, dimethyl 2,6-naphthalene di carboxylate, dimethyl fumarate, dimethyl orthophthalate, dimethylsuccinate, dimethyl glutarate, dimethyl adipate; an acidic monomer having an aliphatic group containing at least 15 carbon atoms; esters and anhydrides of all the aforementioned acids; and mixtures thereof.

[0149] “Polyol” and like terms, as used herein, refers to a compound having two or more hydroxyl groups, such as two, three or four hydroxyl groups. The hydroxyl groups of the polyol may be connected by a bridging group selected from: an alkylene group; an alkenylene group; an alkynylene group; an aralkyne group; arylarylene group, or an arylene group. Suitably the polyol is an organic polyol.

[0150] The polyester material may be formed from any suitable polyol. Suitable polyols include, but are not limited to the following: alkylene glycols, such as ethylene glycol; propylene glycol; diethylene glycol; dipropylene glycol; triethylene glycol; tripropylene glycol; hexylene glycol; polyethylene glycol; polypropylene glycol and neopentyl glycol; hydrogenated bisphenol A; cyclohexanediol; propanediols including 1 ,2-propanediol; 1 ,3-propanediol; butyl ethyl propanediol; 2-methyl-1 ,3- propanediol; and 2-ethyl-2-butyl-1 ,3-propanediol; butanediols including 1 ,4- butanediol; 1 ,3-butanediol; 2,2,4,4-tetraalkyl-1 ,3-cyclobutanediol such as 2, 2,4,4- tetramethyl-1 ,3-cyclobutanediol; and 2-ethyl-1 ,4-butanediol; pentanediols including trimethyl pentanediol and 2-methylpentanediol; cyclohexanedimethanol; hexanediols including 1 ,6-hexanediol; caprolactonediol (for example, the reaction product of epsilon-capro lactone and ethylene glycol); hydroxyalkylated bisphenols; polyether glycols, for example, poly(oxytetramethylene) glycol; trimethylol propane; pentaerythritol; di-pentaerythritol; trimethylol ethane; trimethylol butane; dimethylol cyclohexane; bio-derived polyols such as glycerol, sorbitol; and / or an acidicmonomer having an aliphatic group containing at least 15 carbon atoms and the like or combinations thereof.

[0151] The film forming resin in the packaging coating composition may also be an acrylic modified polyester resin. The acrylic polyester resin may be obtainable by grafting an acrylic polymer and a polyester resin, wherein the polyester resin is obtainable by polymerizing: i) a polyacid component with ii) a polyol component and wherein one of the polyacid component or the polyol component comprises a functional monomer operable to impart functionality on to the polyester resin, such that an acrylic polymer may be grafted with the polyester resin via the use of said functionality.

[0152] The polyacid component or the polyol component of the polyester resin of the acrylic polyester resin comprises a functional monomer operable to impart functionality to the polyester resin. The functionality is such that an acrylic polymer may be grafted onto the polyester resin via the use of said functionality. The functionality may comprise ethylenic unsaturation, carboxylic acid functionality or epoxy functionality. The functionality may be in the backbone of the polyester resin or pendant therefrom.

[0153] The functional monomer may comprise an ethylenically unsaturated monomer, which ethylenically unsaturated monomer may be operable to impart ethylenically unsaturated functionality on the backbone of the polyester resin, or pendant therefrom. The functionality may comprise ethylenic unsaturation, which may be in the backbone of the polyester resin. Suitable functional monomers comprise: maleic acid, maleic anhydride, fumaric acid, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid, aconitic acid, aconitic anhydride, oxalocitraconic acid, oxalocitraconic anhydride, mesaconic acid, mesaconic anhydride, phenyl maleic acid, phenyl maleic anhydride, t-butyl maleic acid, t-butyl maleic anhydride, monomethyl fumarate, monobutyl fumarate, nadic acid, nadic anhydride, methyl maleic acid, methyl maleic anhydride, and / or trimethylolpropane monoallyl ether.

[0154] Where the functional monomer comprises a polyacid, the functional monomer may be present as a proportion of the solid weight of the polyacid component in an amount of from 0.5 to 10 wt.%, such as from 1 to 5 wt.%.

[0155] Where the functional monomer comprises a polyol, the functional monomer may be present as a proportion of the solid weight of the polyol component in an amount of from 0.5 to 10 wt.%, such as from 1 to 5 wt.%.

[0156] The functional monomer of the polyester resin of the acrylic polyester resin may comprise maleic acid, maleic anhydride and / or fumaric acid.

[0157] The polyester resin of the acrylic polyester resin may be modified with acrylic by grafting an acrylic modification polymer onto the polyester resin. This grafting may occur via free radical polymerization, such as by free radical polymerization onto ethylenic unsaturation on the polyester material.

[0158] The acrylic modification polymer may be formed from acrylic monomers. The acrylic modification polymer may be grafted onto the polyester resin by polymerizing acrylic monomers in the presence of the polyester material to form the acrylic polyester resin.

[0159] Various acrylic monomers can be combined to prepare the acrylic modification polymer. Suitable monomers include methyl(meth)acrylate, ethyl(meth)acrylate, butyl(meth)acrylate, cyclohexyl (meth) acrylate; allyl (meth)acrylate; isobornyl (meth)acrylate, hydroxyethyl (meth)acrylate, 2- ethylhexyl(meth)acrylate, (meth)acrylic acid, dimethylamino ethyl methacrylate, butylamino ethyl (meth)acrylate, and / or HEMA phosphate (such as ethylene glycol methacrylate phosphate). Any other acrylic monomers known to those skilled in the art could also be used.

[0160] The term "(meth) acrylate" and like terms are used conventionally and herein to refer to both methacrylate and acrylate.

[0161] A suitable acrylic modification polymer is formed from monomers comprising: methyl (meth)acrylate, ethyl(meth)acrylate, butyl (meth)acrylate, hydroxyethyl (meth)acrylate, (meth)acrylic acid, cyclohexyl (meth)acrylate, allyl (meth)acrylate, dimethylamino ethyl methacrylate, butylamino ethyl (meth)acrylate, and / or HEMA phosphate (such as ethylene glycol methacrylate phosphate).

[0162] The acrylic monomers may comprise a ratio of methacrylate monomers to acrylate monomers of at least 1 :1 , such as at least 2:1 or at least 3:1 or at least 4:1 , such as at least 5:1 . The acrylic monomers may be substantially free of acrylate monomers. By “methacrylate monomers” and “acrylate monomers” with regard to the ratio of these types of monomers in the acrylic monomers of the acrylicmodification polymer, it is meant the total number of methacrylate monomers compared to the total number of acrylate monomers across all the types of acrylic monomer that form the acrylic modification polymer. For example, if the acrylic modification polymer is formed of methylmethacrylate, methyl acrylate and butyl acrylate, then the amount of methylmethacrylate compared to the combined amount of methyl acrylate and butyl acrylate would be at least 5:1 .

[0163] The acrylic monomers may comprise a hydroxyl functional monomer, such as hydroxyethyl (meth)acrylate. The hydroxyl functional monomer may be present by solid weight of the acrylic modification polymer in an amount of from 5 to 40 wt.%, such as from 5 to 30 wt.% or from 10 to 20 wt.%.

[0164] The acrylic modification polymer may also comprise an amount (such as 0 to 30wt.%, by solid weight of the acrylic modification polymer) of non-acrylic monomers. Such non acrylic monomers may include other ethylenically unsaturated monomers, such as styrene, ethylene, propylene, vinyl toluene, butadiene, 1 -octene or isoprene, vinyl esters such as vinyl acetate, and / or acrylic monomers such as (meth)acrylonitrile.

[0165] It has been identified that the acrylic modification polymer may include meth acrylic acid or acrylic acid to impart acid functionality on the acrylic modification polymer. The acid functionality on the acrylic modification polymer may be at least partially neutralized with a neutralization agent.

[0166] The Tg of the acrylic modification polymer (which is a measure of the Tg of the acrylic modification polymer, polymerized as a simple acrylic polymer, not in the presence of (or grafted onto) a polyester resin) may be from 20 to 120°C. The Tg of the acrylic modification polymer can be calculated by the Fox equation as provided in “Coatings of Polymers and Plastics”, Ryntz R. A. and Yaneff P. V, CRC Press, 4 February 2003, page 134.

[0167] Suitable neutralization agents include ammonia or amine functional moieties: methyl ethanolamine, dimethylethanolamine (DMEA), trimethylamine, diethylene triamine.

[0168] The acid functionality on the acrylic modification polymer may be at least 30% neutralized with a neutralization agent. The acid functionality on the acrylic modification polymer may be at least 50% neutralized with a neutralization agent.The acid functionality on the acrylic modification polymer may be at least 75% neutralized with a neutralization agent.

[0169] The packaging coating composition may also comprise a crosslinking material. The coating composition may comprise any suitable crosslinking material. Suitable crosslinking materials will be well known to the person skilled in the art

[0170] The crosslinking material may be operable to crosslink the polyester material. The crosslinking material may be a single molecule, a dimer, an oligomer, a (co)polymer or a mixture thereof. The crosslinking material may be a dimer or trimer.

[0171] Suitable crosslinking materials include but are not limited to: phenolic resins (or phenolformaldehyde resins); aminoplast resins (or triazine-formaldehyde resins); amino resins; epoxy resins; isocyanate resins; beta-hydroxy (alkyl) amide resins; alkylated carbamate resins; polyacids; anhydrides; organometallic acidfunctional materials; polyamines; and / or polyamides and combinations thereof.

[0172] Suitable phenolic resins are those formed from the reaction of a phenol with an aldehyde or a ketone, such as from the reaction of a phenol with an aldehyde, such as from the reaction of a phenol with formaldehyde or acetaldehyde, or even from the reaction of a phenol with formaldehyde. Suitable phenols which may be used to form phenolic resins are phenol, butyl phenol, xylenol and cresol. General preparation of phenolic resins is described in “The Chemistry and Application of Phenolic Resins or Phenoplasts”, Vol V, Part I, edited by Dr Oldring; John Wiley and Sons / Cita Technology Limited, London, 1997. The phenolic resins may be of the resol type. By “resol type” we mean resins formed in the presence of a basic (alkaline) catalyst and optionally an excess of formaldehyde. Suitable commercially available phenolic resins include, but are not limited to those sold under the trade name PHENODUR (RTM) commercially available from Allnex, such as PHENODUR EK-827, PHENODUR VPR1785, PHENODUR PR 515, PHENODUR PR516, PHENODUR PR 517, PHENODUR PR 285, PHENODURPR612 or PHENODUR PH2024; resins sold under the trade name BAKELITE (RTM) commercially available from Sumitomo Bakelite co., ltd., such as BAKELITE 6582 LB, BAKELITE 6535, BAKELITE PF9989 or BAKELITE PF6581 ; SFC 112 commercially available from SI Group; DUREZ (RTM) 33356 commercially available from SHHPP; ARALINK (RTM) 40- 852 commercially available from Bitrez; or combinations thereof.

[0173] Suitable isocyanate resins include, but are not limited to the following: isophorone diisocyanate (IPDI), such as those sold under the trade name DESMODUR (RTM) commercially available from Covestro, for example DESMODUR VP-LS 2078 / 2 or DESMODUR PL 340 or those sold under the trade name VESTANAT (RTM) commercially available from Evonik, for example VESTANAT B 1370, VESTANAT B 118 6A or VESTANAT B 1358 A; blocked aliphatic polyisocyanate based on hexamethylene diisocyanate (HDI), such as those sold under the trade name DESMODUR (RTM) commercially available from Covestro, for example DESMODUR BL3370 or DESMODUR BL 3175 SN, those sold under the trade name DURANATE (RTM) commercially available from Asahi KASEI, for example DURANATE MF-K60X, those sold under the trade name TOLONATE (RTM) commercially available from Vencorex Chemicals, for example TOLONATE D2 or those sold under the trade name TRIXENE (RTM) commercially available from Baxenden, for example TRIXENE-BI-7984 or TRIXENE 7981 ; or combinations thereof.

[0174] The crosslinking material may contain nitrogen. The crosslinking material may be in the form of an amine or amide material. The crosslinking material may comprise a hydroxyl substituted amine or amide material.

[0175] The crosslinking material may comprise a hydroxyalkylamide material, such as a beta-hydroxyalkylamide material.

[0176] The crosslinking material may comprise a commercially available beta- hydroxyalkylamide crosslinking, such as, for example, PRIMID XL-552 (available from EMS); PRIMID QM-1260 (available from EMS Chemie); and N,N,N’,N’- tetrakis(2-hydroxypropyl)adipamide.

[0177] The crosslinking material may be in the form of a urea material. The crosslinking material may comprise a hydroxyl substituted urea material. The crosslinking material may comprise a hydroxy functional alkyl polyurea material.

[0178] The hydroxy functional alkyl polyurea material may comprise a material according to formula (I):

[0179] wherein R comprises an isocyanurate moiety, biuret moiety, allophonate moiety, glycoluril moiety, benzoguanamine moiety, polyetheramine moiety, and / or polymeric moiety different from a polyetheramine and having an Mn of 500 or greater; wherein each R1 is independently a hydrogen, alkyl having a carbon, or a hydroxy functional alkyl having 2 or more carbons and at least one R1 is a hydroxy functional alkyl having 2 or more carbons; and n is 2-6.

[0180] The hydroxy functional alkyl polyurea material may comprise a material according to formula (II):38

[0181] wherein R2 is a substituted or unsubstituted C1 to C36 alkyl group, an aromatic group, an isocyanurate moiety, biuret moiety, allophonate moiety, glycoluril moiety, benzoguanamine moiety, polyetheramine moiety, and / or polymeric moiety different from a polyetheramine and having an Mn of 500 or greater; wherein each R1 is independently a hydrogen, an alkyl having a carbon, or a hydroxy functional alkyl having 2 or more carbons and at least one R1 is a hydroxyl functional alkyl having 2 or more carbons; and n is 2-6.

[0182] Further details of suitable hydroxy functional alkyl polyurea materials are disclosed in PCT patent application WO 2017 / 123955, the entire contents of which are fully incorporated herein by reference.

[0183] Suitable aminoplast resins include those which are a reaction product of a reaction mixture comprising a triazine such as melamine or benzoguanamine and formaldehyde. These condensates may be etherified, typically, with methanol, ethanol, butanol or mixtures thereof. For the chemistry, preparation and use of aminoplast resins, see “The Chemistry and Applications of Amino Crosslinking agents or Aminoplast”, Vol. V, Part 11 , page 21 ft, edited by Dr. Oldring; John Wiley & Sons / Cita Technology Limited, London, 1998. Suitable commercially available aminoplast resins include, but are not limited to, those sold under the trade name MAPRENAL (registered trade mark), such as MAPRENAL MF980 (commercially available from Prefere Resins); those sold under the trade name CYMEL (registeredtrade mark), such as CYMEL 303 and CYMEL 1128 (available from Allnex Industries); and combinations thereof.

[0184] The crosslinking material may comprise material according to formula (HI)wherein Ri represents hydrogen, alkyl (such as C1 to C20 alkyl), aryl (such as C4 to C24 aryl), aralkyl (such as C5 to C25 aralkyl), or — NR6R7; R2 to R7 each independently represent hydrogen, alkyl (such as C1 to C20 alkyl), aryl (such as C4 to C24 aryl), aralkyl (such as C5 to C25 aralkyl) or — CHR8OR9; wherein R8 and R9 each independently represent hydrogen, alkyl (such as C1 to C20 alkyl), aryl (such as C4 to C24 aryl), aralkyl (such as C5 to C25 aralkyl), alkoxyalkyl (such as C2 to C40 alkoxyalkyl) or an alkaryl (such as C5 to C25 alkaryl); wherein at least one of R2 to R5, or R2 to R7 when present, is — CHR8OR9, for example all of R2 to R5, or R2 to R7 when present, may be — CHR8OR9

[0185] In the crosslinking material according to formula (III), R1 may be C1 to C20 alkyl, C4 to C24 aryl, C5 to C25 aralkyl, or — NR6R7; such as C4 to C24 aryl or C5 to C25 aralkyl, or C4 to C24 aryl, such as C4 to C12 aryl, such as C5 aryl.

[0186] In the crosslinking material according to formula (III), R1 may be — NR6R7.

[0187] In the crosslinking material according to formula (III), R2 to R7, when present as applicable, may each be independently hydrogen, C1 to C20 alkyl, C4 to C24 aryl or — CHR8OR9, such as hydrogen, C1 to C20 alkyl or — CHR8OR9, such as hydrogen, C1 to C10 alkyl or — CHR8OR9; such as C1 to C5 alkyl or — CHR8OR9, such as — CHR8OR9.

[0188] In the crosslinking material according to formula (III), R2 to R7, when present as applicable, may each be independently hydrogen, C1 to C20 alkyl, C4 toC24 aryl or — CHR8OR9, such as hydrogen, C1 to C20 alkyl or — CHR8OR9, such as hydrogen, C1 to C10 alkyl or — CHR8OR9; such as C1 to Cs alkyl or — CHR8OR9, such as — CHR8OR9, and Rs may be independently be hydrogen, C1 to C20 alkyl, C4 to C24 aryl, C5 to C25 aralkyl, alkoxyalkyl C2 to C40 alkoxyalkyl or C5 to C25 alkaryl, such as hydrogen, C1 to C20 alkyl, such as hydrogen; and Rg may be hydrogen, C1 to C20 alkyl, C4 to C24 aryl, Cs to C25 aralkyl, alkoxyalkyl C2 to C40 alkoxyalkyl or Cs to C25 alkaryl; such as hydrogen, C1 to C20 alkyl; such as C1 to C20 alkyl, or C1 to C10 alkyl, or C1 to C5 alkyl, such as C1 or C2 alkyl.

[0189] The crosslinking material according to formula (III) may be a reaction product of a reaction mixture comprising a triazine such as melamine or benzoguanamine and formaldehyde. These condensates may be etherified, typically, with methanol, ethanol, butanol or mixtures thereof. For the chemistry, preparation and use of aminoplast resins, see “The Chemistry and Applications of Amino Crosslinking agents or Aminoplast”, Vol. V, Part 11 , page 21 ff. , edited by Dr. Oldring; John Wiley & Sons / Cita Technology Limited, London, 1998.

[0190] The crosslinking material according to formula (III) may comprise melamine or derivatives thereof, such as butylated and / or methylated melamine; and / or benzoguanamine or derivatives thereof, such as butylated and / or methylated benzoguanamine. The crosslinking material according to formula (III) may comprise benzoguanamine or derivatives thereof, such as butylated and / or methylated benzoguanamine.

[0191] The crosslinking material may comprise those which are the reaction product of a reaction mixture comprising a triazine, such as melamine or benzoguanamine, and formaldehyde. The crosslinking material may comprise benzoguanamine or a derivative thereof.

[0192] The benzoguanamine or derivative thereof may comprise commercially available benzoguanamine or derivative thereof. Suitable commercially available benzoguanamines and its derivatives include, but are not limited to benzoguanamine- formaldehyde based materials such as those sold under the trade name CYMEL (registered trade mark), for example CYMEL 1123 (commercially available from Allnex Industries), those sold under the trade name ITAMIN (registered trade mark), for example ITAMIN BG143 (commercially available from Galstaff Multiresine) or those sold under the trade name MAPRENAL (registeredtrade mark), for example, MAPRENAL BF892 and MAPRENAL BF 892 / 68B (commercially available from Prefere Resins); glycoluril based materials, such as those sold under the trade name CYMEL (registered trade mark), for example, CYMEL 1170 and CYMEL 1172 (commercially available from Allnex); and combinations thereof.

[0193] The crosslinking material may be present in the coating composition in any suitable amount.

[0194] The coating composition may comprise at least 0.5 wt.% crosslinking material based on the total solid weight of the coating composition, such as at least 1 wt.%, at least 5 wt.%, at least 10 wt.%, or at least 15 wt.% crosslinking material based on the total solid weight of the coating composition.

[0195] The coating composition may comprise from 0.5 to 90 wt.%, or 1 to 90 wt.%, such as from 1 to 80 wt.%, such as from 1 to 70 wt.%, such as from 1 to 60 wt.%, such as from 1 to 50 wt.%, such as from 1 to 40 wt.%, such as from 1 to 30 wt.%, or even from 1 to 25 wt.% crosslinking material based on the total solid weight of the coating composition. The coating composition may comprise from 5 to 90 wt.%, such as from 5 to 80 wt.%, such as from 5 to 70 wt.%, such as from 5 to 60 wt.%, such as from 5 to 50 wt.%, such as from 5 to 40 wt.%, such as from 5 to 30 wt.%, or even from 5 to 25 wt.% crosslinking material based on the total solid weight of the coating composition. The coating composition may comprise from 10 to 90 wt.%, such as from 10 to 80 wt.%, such as from 10 to 70 wt.%, such as from 10 to 60 wt.%, such as from 10 to 50 wt.%, such as from 10 to 40 wt.%, such as from 10 to 30 wt.%, or even from 10 to 25 wt.%, or 10 to 20 wt.%, crosslinking material based on the total solid weight of the coating composition. The coating composition may comprise from 15 to 90 wt.%, such as from 15 to 80 wt.%, such as from 15 to 70 wt.%, such as from 15 to 60 wt.%, such as from 15 to 50wt.%, such as from 15 to 40 wt.%, such as from 15 to 30 wt.%, or even from 15 to 25wt.% crosslinking material based on the total solid weight of the coating composition.

[0196] The packaging coating compositions may also include an additive comprising oxazolidone groups. For example, the oxazolidone additive may comprise at least two oxazolidone functionalities. The at least two oxazolidone functionalities may both be bonded to a single linking group. The oxazolidone functionalities may also be bonded to at least two connective groups which arebonded to terminal groups. The connective groups may comprise an aromatic group or an aliphatic group and the terminal groups may comprise an epoxy group, an acid group, a hydroxyl group, an amine group, an aromatic group, or an aliphatic group. A structure of the oxazolidone additive is shown in Table 4 below:Table 4Packaging Coating Oxazolidone Structure

[0197] The oxazolidone additive may be present in the packaging coating compositions in an amount as low as 1 wt.%, 1 .5 wt.% 2 wt.%, 2.5 wt.%, 3 wt.%, 3.5 wt.%, 4 wt.%, 4.5 wt.%, 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%, or as high as 11 wt.%, 12 wt.%, 13 wt.%, 14 wt.%, 15 wt.%, 16 wt.%, 17 wt.%, 18 wt.%, 19 wt.%, 20 wt.%, or within any range encompassed by any two of the foregoing values as endpoints, based on the total weight of the packaging coating compositions. For example, the oxazolidone additive may be present in an amount of from 1 wt.% to 8 wt.%, 1 .5 wt.% to 7 wt.%, 2 wt.% to 6 wt.%, 2.5 wt.% to 5 wt.%, 3 wt.% to 4.5 wt.%, or 3.5 wt.% to 4 wt.%.

[0198] The coating composition may be applied as a single layer to an uncoated substrate. For example, the coating composition can be applied to the substrate to form a monocoat. As used herein, a "monocoat" refers to a single coating layer that is free of additional coating layers. Thus, the coating composition can be applied directly to a substrate and cured to form a single layer coating, i.e., a monocoat.

[0199] The coated substrate of the present disclosure may further comprise one or more additional coating layers, such as a second overcoat deposited onto at least a portion of the first coating composition, to form a multi-layer coating such as by applying a topcoat. When a multi-layer coating is formed, the first coating composition can be cured prior to application of additional overcoats, or one or moreof the additional overcoats and the first coating composition can be cured simultaneously. It is appreciated that the second overcoat and additional overcoat can be in solid or liquid form. The coating compositions may be layered underneath a topcoat or series of topcoats to form a stackup. The coating composition may be a first layer applied to a bare substrate as an undercoating or primer. The primer may then have subsequent layers applied on top of it to form a multi-layer coating.

[0200] The packaging coating composition of the present invention may be applied onto a number of substrates. Accordingly, the present disclosure is further directed to a substrate that is coated, at least in part, with a coating deposited from the packaging coating composition described herein. For example, the compositions of the present disclosure are suitable for use as packaging coatings. The application of various pretreatments and coatings to packaging is well established. Such treatments and / or coatings, for example, can be used in the case of metal cans, wherein the treatment and / or coating is used to retard or inhibit corrosion, provide a decorative coating, provide ease of handling during the manufacturing process, and the like. Coatings can be applied to the interior of such cans to prevent the contents from contacting the metal of the container. Contact between the metal and a food or beverage, for example, can lead to corrosion of a metal container, which can then contaminate the food or beverage. This is particularly true when the contents of the can are acidic in nature. The coatings applied to the interior of metal cans also help prevent corrosion in the headspace of the cans, which is the area between the fill line of the product and the can lid; corrosion in the headspace is particularly problematic with food products having a high salt content. Coatings can also be applied to the exterior of metal cans. Certain coatings of the present invention are particularly applicable for use with coiled metal stock, such as the coiled metal stock from which the ends of cans are made (“can end stock”), and end caps and closures are made (“cap / closure stock”). Since coatings designed for use on can end stock and cap / closure stock are typically applied prior to the piece being cut and stamped out of the coiled metal stock, they are typically flexible and extensible. For example, such stock is typically coated on both sides. Thereafter, the coated metal stock is punched. For can ends, the metal is then scored for the “pop-top” opening and the pop-top ring is then attached with a pin that is separately fabricated. The end is then attached to the can body by an edge rolling process. A similar procedure is done for“easy open” can ends. For easy open can ends, a score substantially around the perimeter of the lid allows for easy opening or removing of the lid from the can, typically by means of a pull tab. For caps and closures, the cap / closure stock is typically coated, such as by roll coating, and the cap or closure stamped out of the stock; it is possible, however, to coat the cap / closure after formation. Coatings for cans subjected to relatively stringent temperature and / or pressure requirements should also be resistant to popping, corrosion, blushing and / or blistering.

[0201] Accordingly, the present invention is further directed to a package coated at least in part with any of the coating compositions described above. A “package” is anything used to contain another item, particularly for shipping from a point of manufacture to a consumer, and for subsequent storage by a consumer. A package will be therefore understood as something that is sealed so as to keep its contents free from deterioration until opened by a consumer. The manufacturer will often identify the length of time during which the food or beverage will be free from spoilage, which typically ranges from several months to years. Thus, the present “package” is distinguished from a storage container or bakeware in which a consumer might make and / or store food; such a container would only maintain the freshness or integrity of the food item for a relatively short period. A package according to the present invention can be made of metal or non-metal, for example, plastic or laminate, and be in any form. A suitable package is a laminate tube.Another suitable package is a metal can. The term “metal can” includes any type of metal can, container or any type of receptacle or portion thereof that is sealed by the food / beverage manufacturer to minimize or eliminate spoilage of the contents until such package is opened by the consumer. One type of a metal can is a food can; the term “food can(s)” is used herein to refer to cans, containers or any type of receptacle or portion thereof used to hold any type of food and / or beverage. “Beverage can” may also be used to refer more specifically to a food can in which a beverage is packaged. The term “metal can(s)” specifically includes food cans (including beverage cans) and also specifically includes “can ends” including “E-Z open ends”, which are typically stamped from can end stock and used in conjunction with the packaging of food and beverages. The term “metal cans” also specifically includes metal caps and / or closures such as bottle caps, screw top caps and lids of any size, lug caps, and the like. The metal cans can be used to hold other items aswell, including, but not limited to, personal care products, bug spray, spray paint, and any other compound suitable for packaging in an aerosol can. The cans can include “two piece cans” and “three-piece cans” as well as drawn and ironed one-piece cans; such one piece cans often find application with aerosol products. Packages coated according to the present invention can also include plastic bottles, plastic tubes, laminates and flexible packaging, such as those made from PE, PP, PET and the like. Such packaging could hold, for example, food, toothpaste, personal care products and the like.

[0202] The coating can be applied to the interior and / or the exterior of the package. For example, the coating can be roll coated onto metal used to make a three-piece metal can, can end stock and / or cap / closure stock or sprayed, flow coated, or gravure or roll coated onto a formed two-piece metal can. The coating is applied to a coil or sheet by roll coating; the coating is then cured by radiation and can ends are stamped out and fabricated into the finished product, i.e. , can ends. The coating could also be applied as a rim coat to the bottom of the can; such application can be by roll coating. The rim coat functions to reduce friction for improved handling and protection during the continued fabrication and / or processing of the can. The coating can also be applied to caps and / or closures; such application can include, for example, a protective varnish that is applied before and / or after formation of the cap / closure and / or a pigmented enamel post applied to the cap, particularly those having a scored seam at the bottom of the cap. Decorated can stock can also be partially coated externally with the coating described herein, and the decorated, coated can stock used to form various metal cans.

[0203] It will be appreciated that the coating composition of the present invention is appropriately formulated to be suitable for application to a can end over a score line. The formation of a can end may comprise applying a coating composition to metal coil and curing the coating composition to form a cured film. The coated coil then undergoes pressing, bending and stamping to transform the coil into the can end. The coating should be able to withstand these mechanical requirements. For example, the coating composition may have sufficient flexibility, adhesion to substrate, hardness and / or lubricity.

[0204] The can may comprise a can body and a can end. Suitable cans include, but are not limited to one or more of the following, two-piece cans, three- piece cans and the like. The can may be a beverage can.

[0205] The can may be formed from any suitable material. Suitably, the can may be formed from metal. Suitable metals will be well known to a person skilled in the art. Suitable metals include, but are not limited to the following: steel; tinplate; tinplate pre-treated with a protective material such as chromium, titanium, titanate or aluminum; tin-free steel (TFS); galvanized steel, such as for example electrogalvanized steel; aluminum; aluminum alloy; and combinations thereof. It will be appreciated by a person skilled in the art that the can body and can end of the beverage can may be formed from the same or different materials, such as the same or different metals. Suitably, the can body and can end of the beverage can may be formed from the same material, such as the same metal.

[0206] The can body and / or can end may be made from coiled metal stock. Suitably, at least the can end may be formed from coiled metal stock. Suitably, the coating compositions of the present invention may be applied to coiled metal stock, such as the coiled metal stock from which the ends of cans are made (“can end stock”).

[0207] The coating composition may be applied to the can end stock prior to the can end being cut and stamped out of the coiled metal stock. The can end may be coated on one or both surfaces. As such, the can coil stock may be coated on one or both surfaces prior to the can end being cut and stamped out of the coiled metal stock.

[0208] Advantageously, coating the coiled metal stock on both surfaces thereof may provide sufficient lubricity such that the coating is able to survive the stamping operation.

[0209] The can ends having a score line thereon may be “easy open” can ends, sometimes referred to as “easy open ends” or even “EOEs”.

[0210] Suitably, the score line is applied to the can ends after the can ends have punched from the coated metal stock.

[0211] The can ends, once formed, are suitably attached to a can body. The can end may be attached to the can body by any suitable method. Suitably, the can end may be attached to the can body by an edge rolling process.

[0212] The coating compositions may be applied to at least the internal surface of the can end over a portion of the score line or may be applied over all of the score line

[0213] The coating compositions may be applied to substantially all of or to a portion of the interior surface of the can end, with the proviso that the coating compositions are applied to at least a portion of the interior surface of the can end over at least a portion of the score line. Suitably, the coating compositions may be applied to substantially all of the interior surface of the can end. The coating compositions may be applied to at least a portion of the exterior surface of the can end. The coating compositions may be applied to substantially all of or to a portion of the exterior surface of the can end. Suitably, the coating compositions may be applied to the exterior surface of the can end over at least a portion of the score line. The coating compositions may be applied to at least a portion of the interior and / or exterior surface of the can body.

[0214] The coating compositions may be applied to the beverage can by any suitable method. Methods of applying said coating compositions will be well known to a person skilled in the art. Suitable application methods include, but are not limited to one or more of the following, spray coating, roll coating, dipping and / or electrocoating

[0215] The coating compositions may be applied to any suitable dry film thickness. The coating compositions may be applied to a dry film thickness from 0.1 pm (microns) to 12 pm, suitably from 2 pm to 8 pm, more suitably from 4 pm to 7 pm, or even from 4 pm to 6 pm.

[0216] The packaging coated articles contemplated by the present disclosure may demonstrate high adhesion. For example, the coated articles may have an adhesion of 0B or higher, 1 B or higher, 2B or higher, 3B or higher, 4B or higher, or 5B after the acetic acid test according to ASTM D3359-22.

[0217] The present disclosure also contemplates a method for forming an article coated with the packaging coating compositions. The coating compositions may be applied to the substrate, or a portion thereof, as a single layer or as part of a multi-layer system. Suitable substrates include aluminum, tinplate, tin-free steel, a food package, a beverage package, or a metal can.

[0218] The coating composition may be applied as a single layer. The coating compositions may be applied to an uncoated substrate. For the avoidance of doubt an uncoated substrate extends to a surface that is cleaned prior to application. The coating compositions may be applied on top of another paint layer as part of a multilayer system. For example, the coating composition may be applied on top of a primer. The coating compositions may form an intermediate layer or a topcoat layer. The coating composition may be applied as the first coat of a multi coat system. The coating composition may be applied as an undercoat or a primer. The second, third, fourth etc. coats may comprise any suitable paint such as those containing, for example, epoxy resins; polyester resins; polyurethane resins; polysiloxane resins; hydrocarbon resins or combinations thereof. The second, third, fourth etc. coats may comprise polyester resins. The second, third, fourth etc. coats may be a liquid coating or a powder coating.

[0219] It will be appreciated by a person skilled in the art that the coating composition may be applied before or after forming the article, such as the packaging. For example, the coating composition may be applied to metal substrate which is then shaped and formed into a metal article, or the coating composition may be applied to the preformed article. The coating compositions may be applied to a substrate once or multiple times.

[0220] The coating compositions may be applied to the substrate by any suitable method. Methods of applying the coating compositions will be well known to a person skilled in the art. Suitable application methods for the coating compositions include but are not limited to the following: electrocoating; spraying; electrostatic spraying; dipping; rolling; brushing; and the like.EXAMPLESI. Synthesis ExamplesA. Synthesis of Isocyanate Prepolymer

[0221] Isocyanate-terminated prepolymers were prepared by reacting an excess of a polyisocyanate with a polyol or an alcohol at 60-90°C in the presence of a urethane catalyst, such as dibutyltin dilaurate (DBTDL).

[0222] To a suitable, 4-necked flask equipped with a motor driven stainless steel stir blade, a water-cooled condenser, a nitrogen blanket, and a heating mantle with a thermometer connected through a temperature feedback control device, isophorone diisocyanate (IPDI, commercially available from Covestro LLC) and DBTDL were added. The reaction mixture was heated to 60-80°C. Then polyol or alcohol was added into reaction mixture over 1 hours. After addition, the reaction mixture was held at 60 to 80°C until the isocyanate equivalent weight (NCO EQ Wt) measured was stalled.

[0223] The titration was performed with a Metrohm 888 Titrando. The titration reagent was 20 ml of dibutylamine and 980 ml of tetrahydrofuran, and a 0.2 N HCI Solution in 0.2 N isopropanol.Table 5Synthesis of Isocyanate Prepolymer

[0224] The prepolymers provided in the Table above were formed and characterized. Their structures are shown below.Table 6Structures of PrepolymersB. Synthesis of oxazolidone

[0225] The oxazolidone modified resin was made according to the following procedure. To a suitable 4-necked flask equipped with a motor driven stainless steel stir blade, a water-cooled condenser, a nitrogen blanket, and a heating mantle with a thermometer connected through a temperature feedback control device, charge 1 was added. The reaction mixture was heated to 170 to 175°C. Then charge 2 was added into reaction mixture dropwise over 1 hour. After addition, the reaction mixture was held at 170 to 180°C until IR spectroscopy showed the absence of the characteristic NCO band (2269 cm-1) using the Thermo Scientific Nicolet iS5 FT-IR. Then, the reaction mixture was cooled to 120°C and poured out from the flask to a metal can to form a powder resin.Table 7 Synthesis of Oxazolidone

[0226] Eponex 1510, Epon 828, and TSR-400 are commercially available from Hexion Specialty Chemicals and tetrabutylphosphonium bromide is commercially available from Sigma Aldrich.

[0227] The structures of the compounds synthesized by the Example above are provided in the following table.Table 8Structures of CompoundsC. Synthesis of OH Functional Oxazolidone

[0228] To a suitable 4-necked flask equipped with a motor driven stainless steel stir blade, a water-cooled condenser, a nitrogen blanket, and a heating mantle with a thermometer connected through a temperature feedback control device, charge 1 and 2 were added. The reaction mixture was heated to 120°C. The reaction mixture was held until AV is less than 2. Then the solvent was distilled under vacuum to form a powder resin or the reaction mixture was cooled down to 40°C and poured out.Table 9Synthesis of Hydroxyl Functional Oxazolidone

[0229] The structures of the compounds synthesized by the Example above are provided in the following table.Table 10Structures of CompoundsD. Synthesis of hydroxyl functional oxazolidone for liquid application

[0230] To a suitable 4-necked flask equipped with a motor driven stainless steel stir blade, a water-cooled condenser, a nitrogen blanket, and a heating mantle with a thermometer connected through a temperature feedback control device, charge 1 was added. The reaction mixture was heated to 170 to 175°C. Then charge 2 was added into reaction mixture dropwise over 1 hour. After addition, the reaction mixture was held at 170 to 180°C until IR spectroscopy showed the absence of the characteristic NCO band (2269 cm'1) using the Thermo Scientific Nicolet iS5 FT-IR. Then, the reaction mixture was cooled to 120°C, charge 3 was added into reaction mixture and hold until AV is less than 2. Then the reaction mixture was cooled down to 40°C and poured out.Table 11Synthesis of Hydroxyl Functional Oxazolidone

[0231] The structures of the compounds synthesized by the Example above are provided in the following table.Table 12E. Synthesis of hydroxyl functional oxazolidone for powder application

[0232] To a suitable 4-necked flask equipped with a motor driven stainless steel stir blade, a water-cooled condenser, a nitrogen blanket, and a heating mantle with a thermometer connected through a temperature feedback control device, charge 1 was added. The reaction mixture was heated to 170 to 175°C. Then charge 2 was added into reaction mixture dropwise for 1 hour. After addition, the reaction mixture was held at 170 to 180°C until IR spectroscopy showed the absence of the characteristic NCO band (2269 cm'1) using the Thermo Scientific Nicolet iS5 FT-IR. Then, the reaction mixture was cooled to 120°C, charge 3 was added into reaction mixture and hold until AV is less than 2. The reaction mixture was distilled under vacuum to remove solvent and poured out to form a powder resin.Table 13Synthesis of Hydroxyl Functional Oxazolidone

[0233] The structures of the compounds synthesized by the Example above are provided in the following table.Table 14F. Synthesis of carboxylic acid functional oxazolidone for powder coatings

[0234] The acid functional oxazolidone resin was formed according to the following procedure. To a suitable 4-necked flask equipped with a motor driven stainless steel stir blade, a water-cooled condenser, a nitrogen blanket, and a heating mantle with a thermometer connected through a temperature feedback control device, charge 1 was added. The reaction mixture was heated to 170 to 175°C. Then Charge 2 was added into reaction mixture dropwise for 1 hour. After addition, the reaction mixture was held at 170 to 180°C until IR spectroscopy showed the absence of the characteristic NCO band (2269 cm'1) using the Thermo Scientific Nicolet iS5 FT-IR. Then, the reaction mixture was cooled to 100°C. Charge 3 wasadded into reaction mixture and hold at 150 °C until AV is less than 2 was obtained with a Metrohm 888 Titrando using a 0.1 N KOH solution in methanol as the reagent (3 to 4 hours). Then charge #4 was added into reaction mixture. The reaction mixture was heated to 150 °C and hold until the IR spectroscopy showed the absence of the characteristic epsilon-caprolactone band (850 and 860 cm-1) using the Thermo Scientific Nicolet iS5 FT-IR. Then charge 5 was added into reaction mixture. The reaction mixture was hold at 150 °C until IR spectroscopy showed the absence of the characteristic anhydride band (1768 cm-1). The reaction mixture was distilled under vacuum to remove solvent and poured out to form a powder resin.Table 15Synthesis of acid functional oxazolidone

[0235] The structures of the compounds synthesized by the Example above are provided in the following table.Table 16Structures of CompoundG. Synthesis of carboxylic acid functional oxazolidone for liquid coatings

[0236] The acid functional oxazolidone resin was formed according to the following procedure. To a suitable 4-necked flask equipped with a motor driven stainless steel stir blade, a water-cooled condenser, a nitrogen blanket, and a heating mantle with a thermometer connected through a temperature feedback control device, charge #1 was added. The reaction mixture was heated to 170 to 175°C. Then Charge 2 was added into reaction mixture dropwise for 1 hour. After addition, the reaction mixture was held at 170 to 180°C until IR spectroscopy showed the absence of the characteristic NCO band (2269 cm-1) using the Thermo Scientific Nicolet iS5 FT-IR. Then, the reaction mixture was cooled to 100°C. Charge 3 was added into reaction mixture and hold at 150 °C until AV is less than 2 was obtained with a Metrohm 888 Titrando using a 0.1 N KOH solution in methanol as the reagent (3 to 4 hours). Then charge #4 were added into reaction mixture. The reaction mixture was heated to 150 °C and hold until the IR spectroscopy showed the absence of the characteristic e-caprolactone band (850 and 860 cm-1 ) using the Thermo Scientific Nicolet iS5 FT-IR. Then charge 5 was added into reaction mixture. The reaction mixture was hold at 150°C until IR spectroscopy showed the absence of the characteristic anhydride band (1768 cm-1). The reaction mixture was cooled down and poured out.Table 17Synthesis of carboxylic acid functional oxazolidone

[0237] The structures of the compounds synthesized by the Example above are provided in the following table.Table 18Structures of CompoundH. Synthesis of oxazolidone functional acrylic for powder coatings

[0238] i. Carboxylic Oxazolidone Functional Acrylic:

[0239] The oxazolidone resin was formed according to the following procedure. To a suitable 4-necked flask equipped with a motor driven stainless steel stir blade, a water-cooled condenser, a nitrogen blanket, and a heating mantle with a thermometer connected through a temperature feedback control device, charge #1 was added. The reaction mixture was heated to reflux (120°C) with stirring. Charge 2 was mixed and added into reactor over 210 minutes. 15 minutes after charge 2, charge 3 was added into reactor over 180 minutes. When addition of charge 3 were completed, charge 4 was used to rinse charge 3. When addition of charge 2 were completed, charge 5 was used to rinse charge 2. After addition of charge 4 and charge 5, A stirring was continued for 90 minutes at reflux. After holding completed, vacuum distillation was set up to remove the solvent. The oxazolidone functional acrylic powder resin was obtained and the Mw is 31 ,000.Table 19Synthesis of carboxylic oxazolidone functional acrylic for powder

[0240] The structures of the compounds synthesized in the Example above are provided in the following table.Table 20Structures of Compound

[0241] ii. Mono-IPDI Capped Oxazolidone:

[0242] The mono-lPDI capped resins were made according to the following procedure. To a suitable 4-necked flask equipped with a motor driven stainless steel stir blade, a water-cooled condenser, a nitrogen blanket, and a heating mantle with a thermometer connected through a temperature feedback control device, charge 1 was added. The reaction mixture was heated to 175 ~180°C. Then charge 2 was added into reaction mixture dropwise over 1 hour. After addition, the reaction mixture was held at 180 ~185°C until IR spectroscopy showed the absence of the characteristic NCO band (2269 cm'1) using the Thermo Scientific Nicolet iS5 FT-IR. An aliquot sample was taken to measure Epoxy Equivalent Weight (EEW) to calculate required amount of charge 3. Then, the reaction mixture was cooled to 120°C and charge 3 was added. When temperature dropped, charge 4 was added. The reaction mixture was held at 130 °C until acid value (AV) reached to less than 5. To synthesize mono-lPDI capped oxazolidone resin, the reaction mixture was further cooled to 80°C and charge 5 was added. Charge 6 was added into reaction mixture dropwise over 2 hours at 80°C. After addition, the reaction mixture was held at 80°C until IR spectroscopy showed the absence of the characteristic NCO band (2269 cm’1) using the Thermo Scientific Nicolet iS5 FT-IR. At 80°C, the resins were poured out from the flask to a metal can to form a mono-lPDI capped powder resin. The resin’s molecular weight as determined by GPC was 32363.Table 20ASynthesis of Mono-IPDI Capped Oxazolidone

[0243] The structure of the compound from Example S19 is provided below.II. E-Coat Compositions ExamplesA. Oxazolidone in a Cationic Acrylic E-coat SystemSynthesis of Aminated Oxazolidone Epoxy (Additive 1 ):

[0244] A cationic oxazolidone-containing additive was prepared in the following manner from the materials included in Table 21 . Materials 1-2 were charged into a reaction vessel and heated under a nitrogen atmosphere to 60°C. Material 3 was added and the reaction was allowed to exotherm to around 100°C. When the reaction reached 100°C, a one-hour hold was started. Epoxy equivalentweight was then checked and found to be infinite (all epoxy consumed) after the one- hour time period. Material 4 was then added to the mixture with mild agitation followed by Material 5. Mixing then occurred for 1 hour followed by pour out.Table 21Components in Additive 1 :Formulation Results:

[0245] The water-dispersed aminated oxazolidone epoxy (additive 1 ) was then evaluated by being added to a commercial PPG cationic acrylic E-coat system, Powercron 935 (P935) at an overall bath solids of 15%, electrodeposited on bare cold rolled steel, and evaluated for corrosion performance in neutral salt fog (ASTM B117-19) in triplicate after 1000 hours by measuring scribe creep (Table 22). While a 1% additive loading provided poorer scribe creep vs. a 0% loading (23.5mm vs 19.9mm, respectively), additive loadings of 4.5% (10.2mm) and 10% (9.3mm) both provided improved results vs the control (0% loading).Table 22Formulation and Corrosion Results:B. Oxazolidone in a Cationic Epoxy E-coat SystemSynthesis of a Blocked Polvisocvanate Curing Agent (Crosslinker)

[0246] A blocked polyisocyanate curing agent was prepared in the following manner: Components 2-5 listed in Table 23, below, were mixed in a flask set up for total reflux with stirring under nitrogen. The mixture was heated to a temperature of 30°C, and Component 1 was added dropwise so that the temperature increased due to the reaction exotherm and was maintained under 100°C. After the addition of Component 1 was complete, a temperature of 100°C was established in the reaction mixture and the reaction mixture held at temperature until no residual isocyanate was detected by IR spectroscopy. Component 6 was then added, and the reaction mixture was allowed to stir for 30 minutes at 100°C before cooling to ambient temperature and poured out.Table 23Synthesis of Blocked Polyisocyanate Curing Agent (Crosslinker):C. Synthesis of an Oxazolidone-Containing Cationic Epoxy E-coat Polymer

[0247] Components 1 -6 listed in Table 8, below, were mixed in a flask set up for total reflux with stirring under nitrogen. The mixture was heated to a temperature of 130°C and allowed to exotherm (175°C maximum). A temperature of 145°C was established in the reaction mixture and the reaction mixture was then held for 2 hours. Component 7 was introduced slowly while allowing the mixture to cool to125°C followed by the addition of Component 8. A temperature of 105°C was established, and Components 10 and 1 1 were then added to the reaction mixture quickly (sequential addition) and the reaction mixture was allowed to exotherm. A temperature of 120°C was established and the reaction mixture held for 1 hour. The product was then poured into a pre-mixed solution of Components 12-13 to form a resin dispersion, and the resin dispersion was stirred for 1 hour. Component 14 was then introduced over 30 minutes to further dilute the resin dispersion, followed by the addition of Component 15. The free MIBK in the resin dispersion was removed from the dispersion under vacuum at a temperature of 60-70°CTable 24Synthesis of Oxazolidone-Containing Cationic Epoxy E-coat PolymerFormulation Results:

[0248] The polymer in Table 23 was evaluated as a ‘clear’ formulation (pigmentation-free) at 33% total bath solids. Two PPG commercial systems were also evaluated as controls (Powercron 10X & Fram E-coat II). All systems were electrodeposited on C700 (zinc phosphate) pretreated cold rolled steel andevaluated for corrosion performance in neutral salt fog (ASTM B117-19) in duplicate after 1000 hours by measuring scribe creep (Table 24). Incorporation of oxazolidone in the main electrocoat polymer provided improved scribe corrosion results vs. commercial systems that do not contain this moiety.Table 25Formulation and Corrosion Results:III. Powder Coating Compositions ExamplesA. Preparation of Coating Compositions utilizing oxazolidones with one or both terminal epoxy groups reacted with a mono-isocyanate

[0249] Each of the components listed in the table below were weighed in a container and mixed in a prism high-speed mixer for 30 seconds at 3500 RPM to form a dry homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19mm twin-screw extruder with an aggressive screw configuration and a speed of 500 RPM. The first zone was set at 30°C, and the second, third, and fourth zones were set at 110°C. The feed rate was such that a torque of 45-55% was observed on the equipment. Upon exiting the extruder, the mixtures were dropped onto a set of chill rolls to cool and re-solidify the mixtures into solid chips. The chips were weighed and 0.15 wt.% of Aerosil 200, based on the total weight o fthe composition was added before milling in a Mikro ACM®-1 Air Classifying Mill to obtain a particle size of 5 to 90 microns with a majority of the particles being from 20 to 50 microns and an average particle size of approximately 27-32 microns as determined by dynamic light scattering measured through Mie scattering and Fraunhofer diffraction technique as per ISO 13320-1 practice. The resulting coating compositions for each Example were solid particulate powder coating compositions that were free flowing.Table 26Preparation of powder coatings in gramsApplication

[0250] The powder coating compositions prepared above were applied with an Encore Nordson powder coating cup gun at 75kV, 15mA restriction, 10 psi atomizing and 10 psi conveying flow air. The coating thickness was between 64 pm to 83 pm for the single coat compositions. The coatings were cured at 375°F for 20 minutes to form a single coating layer. Substrates coated are listed below with testing.Testing

[0251] Comparative corrosion examples were tested as per B117 ASTM salt spray corrosion and SAE J2334 cyclic corrosion exposure with a scribe cut down to middle of a panel exposing metal on 4in x 6in B117 corrosion test panels and 4in x Sin cyclic corrosion test panels. Panel substrate and pretreatment types are listed with the corrosion results. After testing the panels were scraped free of loose coating and corrosion products under a warm water flow. The exposed metal and corrosion product scribe creep was measured as total scribe creep across the exposed area 90° to the scribe line. An average of 10 readings on two panels was reported in millimeters total scribe creep average is reported in the tables below for cyclic corrosion and 5 readings per panel for B117 panels.Table 27500 Hours B117 Corrosion TestingSubstrate | ExampleTable 28768 Hours B117 Corrosion TestingTable 29768 Hours B117 Corrosion TestingTable 3040 Cycles SAE J2334 Cyclic Corrosion TestingTable 31Additional Testing B1000 P99X ACT substrate

[0252] The results show improved B1 17 salt spray scribe corrosion and SAE J2334 corrosion in Examples PC2 and PC3 over PC1 with one epoxy functional group “capped” with a oxazoliodne group and with both epoxy functional groups “capped” with oxazolidone groups. The oxazolidone additive is essentially “nonfunctional” and does not participate in cross-linking or participates with limited (mono-functional) ability to cross-link. The oxazolidone containing oligomer with terminal oxazolidone groups is now essentially an anti-corrosion additive when nonfunctionalB. Preparation of Coating Compositions utilizing oxazolidone epoxy group end capping with a mono-isocyanate

[0253] Each of the components listed in the table below were weighed in a container and mixed in a prism high-speed mixer for 30 seconds at 3500 RPM to form a dry homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19mm twin-screw extruder with an aggressive screw configuration and a speed of 500 RPM. The first zone was set at 30°C, and the second, third, and fourth zones were set at 110°C. The feed rate was such that a torque of 45-55% was observed on the equipment. Upon exiting the extruder, the mixtures were dropped onto a set of chill rolls to cool and re-solidify the mixtures into solid chips. The chips were weighed and 0.15% of Aerosil 200 was added before milling in a Mikro ACM®- 1 Air Classifying Mill to obtain a particle size of 5 to 90 microns with a majority of the particles being from 20 to 50 microns and an average particle size of approximately 27-32 microns. The resulting coating compositions for each Example were solid particulate powder coating compositions that were free flowing.Table 32Preparation of powder coatings in grams|| 100 | 100 | 100 | 100 | 100 | 100 | 100 |Application

[0254] The cured powder coating compositions prepared above were applied with an Encore Nordson powder coating cup gun at 75kV, 15mA restriction, 10 psi atomizing and 10 psi conveying flow air. The coating thickness was between 64 pm to 83 pm for the single coat compositions. The coatings were cured 375°F for 20 minutes to form a single coating layer. Substrates coated are listed below with testing.Testing

[0255] Comparative corrosion examples were tested as per B117 ASTM salt spray corrosion with a scribe cut down to middle of a panel exposing metal on 4inX6in B1 17 corrosion test panels. Panel substrate and pretreatment types are listed with the corrosion results. After testing the panels were scraped free of lose coating and corrosion products under a warm water flow. The exposed metal and corrosion product scribe creep was measured as total scribe creep across the exposed area 90° to the scribe line. An average of 5 readings on two panels was reported in millimeters total scribe creep average is reported in the tables below.Table 33500 Hours B117 Corrosion TestingTable 34744 Hours B117 Corrosion TestingTable 351200 Hours B1 17 Corrosion TestingTable 36Additional Testing B1000 P99X ACT substrate

[0256] The results show improved B117 salt spray scribe corrosion on in examples PC5, PC6, PC7, PC8, PC9 AND PC10 over control PC4 with one epoxy functional group “capped” with a oxazolidone group and with both epoxy functional groups “capped” with oxazolidone groups formed by reacting the end group epoxies with a mono-isocyanate. This shows that corrosion performance can be enhanced with limited to essentially no epoxy functional groups to be incorporated with in the polymer cross-linked network down to a 1 % loading. The oxazolidone containing oligomer with terminal oxazolidone groups can essentially act as an anti-corrosion additive.C. Preparation of Coating Compositions utilizing IPDI based oxazolidone with the end group epoxys reacted with mono-isocyanate

[0257] Each of the components listed in the table below were weighed in a container and mixed in a prism high-speed mixer for 30 seconds at 3500 RPM to form a dry homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19mm twin-screw extruder with an aggressive screw configuration and a speed of 500 RPM. The first zone was set at 30°C, and the second, third, and fourth zones were set at 110°C. The feed rate was such that a torque of 45-55% was observed on the equipment. Upon exiting the extruder, the mixtures were dropped onto a set of chill rolls to cool and re-solidify the mixtures into solid chips. The chips were weighed and 0.15% of Aerosil 200 was added before milling in a Mikro ACM®- 1 Air Classifying Mill to obtain a particle size of 5 to 90 microns with a majority of the particles being from 20 to 50 microns and an average particle size of approximately 27-32 microns. The resulting coating compositions for each Example were solid particulate powder coating compositions that were free flowing.Table 37Preparation of powder coatings in gramsApplication

[0258] The cured powder coating compositions prepared above were applied with an Encore Nordson powder coating cup gun at 75kV, 15mA restriction, 10 psi atomizing and 10 psi conveying flow air. The coating thickness was between 64 pm to 83 pm for the single coat compositions. The coatings were cured 375°F for 20 minutes to form a single coating layer. Substrates coated are listed below with testing.Testing

[0259] Comparative corrosion examples were tested as per B117 ASTM salt spray corrosion with a scribe cut down to middle of a panel exposing metal on 4inX6in B1 17 corrosion test panels. Panel substrate and pretreatment types are listed with the corrosion results. After testing the panels were scraped free of lose coating and corrosion products under a warm water flow. The exposed metal and corrosion product scribe creep was measured as total scribe creep across theexposed area 90° to the scribe line. An average of 5 readings on two panels was reported in millimeters total scribe creep average is reported in the tables below.Table 38500 Hours B117 Corrosion TestingTable 39768 Hours B117 Corrosion TestingTable 40Additional Testing B1000 P99X ACT substrate

[0260] There is improved B117 salt spray scribe corrosion in Examples PC12, PC13, PC14, and PC15 compared to Example PC1 1 . In these examples one epoxy functional group was “capped” by reacting with a mono-isocyanate for one example and for a second example both epoxy functional groups were “capped” with a monoisocyanate. This more aliphatic oxazolidone shows that corrosion performance can be enhanced with limited to essentially no epoxy functional groups in a structure that is more aliphatic.D. Preparation of Coating Compositions utilizing oxazolidone di-epoxy with the epoxy groups removed by a reaction with a mono-acid

[0261] Each of the components listed in the table below were weighed in a container and mixed in a prism high-speed mixer for 30 seconds at 3500 RPM to form a dry homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19mm twin-screw extruder with an aggressive screw configuration and aspeed of 500 RPM. The first zone was set at 30°C, and the second, third, and fourth zones were set at 110°C. The feed rate was such that a torque of 45-55% was observed on the equipment. Upon exiting the extruder, the mixtures were dropped onto a set of chill rolls to cool and re-solidify the mixtures into solid chips. The chips were weighed and 0.15% of Aerosil 200 was added before milling in a Mikro ACM®- 1 Air Classifying Mill to obtain a particle size of 5 to 90 microns with a majority of the particles being from 20 to 50 microns and an average particle size of approximately 27-32 microns. The resulting coating compositions for each Example were solid particulate powder coating compositions that were free flowing.Table 41Preparation of powder coatings in gramsApplication

[0262] The cured powder coating compositions prepared above were applied with an Encore Nordson powder coating cup gun at 75kV, 15mA restriction, 10 psi atomizing and 10 psi conveying flow air. The coating thickness was between 64 pm to 83 pm for the single coat compositions. The coatings were cured 375°F for 20 minutes to form a single coating layer. Substrates coated are listed below with testing.Testing

[0263] Comparative corrosion examples were tested as per B117 ASTM salt spray corrosion with a scribe cut down to middle of a panel exposing metal on 4inX6in B1 17 corrosion test panels. Panel substrate and pretreatment types arelisted with the corrosion results. After testing the panels were scraped free of lose coating and corrosion products under a warm water flow. The exposed metal and corrosion product scribe creep was measured as total scribe creep across the exposed area 90° to the scribe line. An average of 5 readings on two panels was reported in millimeters total scribe creep average is reported in the tables below.Table 42500 Hours B117 Corrosion TestingTable 43500 Hours B117 Corrosion TestingTable 44768 Hours B117 Corrosion TestingTable 451296 Hours B1 17 Corrosion Testing

[0264] The results show improved B117 salt spray scribe corrosion on in Examples PC17 and PC18 over PC16 with the epoxy end groups reacted off with a mono-acid but with an all aliphatic structure for the di-epoxy oxazolidone. With this structure, performance can be enhanced with limited to essentially no epoxy functional groups to be incorporated with in the polymer cross-linked network. The oxazolidone containing oligomer with the terminal epoxy groups reacted off with anacid is now essentially an anti-corrosion additive that is not cross-linked into the polymer networks. The secondary hydroxy group does not participate in the crosslinking reaction.E. Preparation of urethane cross-linked powder Coating Compositions utilizing diepoxy oxazolidones with the epoxy group reacted with a mon-acid

[0265] Each of the components listed in the table below were weighed in a container and mixed in a prism high-speed mixer for 30 seconds at 3500 RPM to form a dry homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19mm twin-screw extruder with an aggressive screw configuration and a speed of 500 RPM. The first zone was set at 30°C, and the second, third, and fourth zones were set at 110°C. The feed rate was such that a torque of 45-55% was observed on the equipment. Upon exiting the extruder, the mixtures were dropped onto a set of chill rolls to cool and re-solidify the mixtures into solid chips. The chips were weighed and 0.15% of Aerosil 200 was added before milling in a Mikro ACM®- 1 Air Classifying Mill to obtain a particle size of 5 to 90 microns with a majority of the particles being from 20 to 50 microns and an average particle size of approximately 27-32 microns. The resulting coating compositions for each Example were solid particulate powder coating compositions that were free flowing.Table 46Preparation of powder coatings in gramsApplication

[0266] The cured powder coating compositions prepared above were applied with an Encore Nordson powder coating cup gun at 75kV, 15mA restriction, 10 psi atomizing and 10 psi conveying flow air. The coating thickness was between 64 pm to 83 pm for the single coat compositions. The coatings were cured 375°F for 20 minutes to form a single coating layer. Substrates coated are listed below with testing.Testing

[0267] Comparative corrosion examples were tested as per B117 ASTM salt spray corrosion with a scribe cut down to middle of a panel exposing metal on 4inX6in B1 17 corrosion test panels. Panel substrate and pretreatment types are listed with the corrosion results. After testing the panels were scraped free of lose coating and corrosion products under a warm water flow. The exposed metal and corrosion product scribe creep was measured as total scribe creep across the exposed area 90° to the scribe line. An average of 5 readings on two panels was reported in millimeters total scribe creep average is reported in the tables below.Table 47500 Hours B117 Corrosion TestingTable 48500 Hours B117 Corrosion TestingTable 491296 Hours B1 17 Corrosion TestingTable 50Additional Testing B1000 P99X ACT substrate

[0268] The results show improved B117 salt spray scribe corrosion with the more aliphatic PC21 and PC22 but no improvement in aromatic example PC20 in these urethane cross-linked powder coating formulations. These formulations have been modified with hydroxyl functional oxazolidones produced by ring opening the di-epoxy oxazolidones with benzoic acid leaving a secondary hydroxyl for crosslinking. The oxazolidone additives can be cross-linked into the system with hydroxy functionality and provide corrosion resistance improvement when the structure is more aliphatic in nature.F. Preparation of powder coatings with oxazolidone di-epoxy structures reacted with a mono-acid to remove the epoxy functionality

[0269] Each of the components listed in the table below were weighed in a container and mixed in a prism high-speed mixer for 30 seconds at 3500 RPM to form a dry homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19mm twin-screw extruder with an aggressive screw configuration and a speed of 500 RPM. The first zone was set at 30°C, and the second, third, and fourth zones were set at 110°C. The feed rate was such that a torque of 45-55% was observed on the equipment. Upon exiting the extruder, the mixtures were dropped onto a set of chill rolls to cool and re-solidify the mixtures into solid chips. The chips were weighed and 0.15% of Aerosil 200 was added before milling in a Mikro ACM®- 1 Air Classifying Mill to obtain a particle size of 5 to 90 microns with a majority of the particles being from 20 to 50 microns and an average particle size of approximately 27-32 microns. The resulting coating compositions for each Example were solid particulate powder coating compositions that were free flowing.Table 51Preparation of powder coatings in gramsApplication

[0270] The cured powder coating compositions prepared above were applied with an Encore Nordson powder coating cup gun at 75kV, 15mA restricted, 10 psi atomizing and 10 psi conveying flow air. The coating thickness was between 64 pm to 83 pm for the single coat compositions. The coatings were cured 375°F for 20 minutes to form a single coating layer. Substrates coated are listed below with testing.Testing

[0271] Comparative corrosion examples were tested as per B117 ASTM salt spray corrosion with a scribe cut down to middle of a panel exposing metal on 4inX6in B1 17 corrosion test panels. Panel substrate types are listed with the corrosion results. After testing the panels were scraped free of lose coating and corrosion products under a warm water flow. The exposed metal and corrosion product scribe creep was measured as total scribe creep across the exposed area90° to the scribe line. An average of 5 readings on two panels was reported in millimeters total scribe creep average is reported in the tables below.Table 52500 Hours B117 Corrosion Testing

[0272] The results show improved B117 salt spray scribe corrosion with PC24, PC25, and PC26 versus the control PC23 with all aromatics, IPDI / aromatic and all aliphatic benzoic acid ring opened epoxy groups. The oxazolidones are essentially non-functional and used as additives to improve corrosion resistance in a primid cured polyester single coat composition.G. Preparation of Coating Compositions utilizing an acrylic oxazolidone produced from an oxazolidone acrylate monomer

[0273] Each of the components listed in the table below were weighed in a container and mixed in a prism high-speed mixer for 30 seconds at 3500 RPM to form a dry homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19mm twin-screw extruder with an aggressive screw configuration and a speed of 500 RPM. The first zone was set at 30°C, and the second, third, and fourth zones were set at 110°C. The feed rate was such that a torque of 45-55% was observed on the equipment. Upon exiting the extruder, the mixtures were dropped onto a set of chill rolls to cool and re-solidify the mixtures into solid chips. The chips were weighed and 0.15% of Aerosil 200 was added before milling in a Mikro ACM@- 1 Air Classifying Mill to obtain a particle size of 5 to 90 microns with a majority of the particles being from 20 to 50 microns and an average particle size of approximately 27-32 microns. The resulting coating compositions for each Example were solid particulate powder coating compositions that were free flowing.Table 53 Preparation of powder coatings in grams | ExampleApplication

[0274] The cured powder coating compositions prepared above were applied with an Encore Nordson powder coating cup gun at 75kV, 15mA restricted, 10 psi atomizing and 10 psi conveying flow air. The coating thickness was between 64 pm to 83 pm for the single coat compositions. The coatings were cured 375°F for 20 minutes to form a single coating layer. Substrates coated are listed below with testing.Testing

[0275] Comparative corrosion examples were tested as per B117 ASTM salt spray corrosion with a scribe cut down to middle of a panel exposing metal on 4inX6in B1 17 corrosion test panels. Panel substrate and pretreatment types are listed with the corrosion results. After testing the panels were scraped free of lose coating and corrosion products under a warm water flow. The exposed metal and corrosion product scribe creep was measured as total scribe creep across the exposed area 90° to the scribe line. An average of 5 readings on two panels was reported in millimeters total scribe creep average is reported in the tables below. Testing film build ranges for corrosion testing of single coats are 70 to 85um.Table 54500 Hours B117 Corrosion TestingTable 55744 Hours B117 Corrosion TestingTable 561296 Hours B1 17 Corrosion TestingTable 57Additional Testing B1000 P99X ACT substrate

[0276] The results show improved B117 salt spray scribe corrosion when utilizing and oxazolidone containing acrylic polymer as an anti-corrosion additive in a powder coating.H. Preparation of Coating Compositions utilizing poly THF 650 to prepare an isocyanate prepolymer based oxazolidone with epoxy functionality

[0277] Each of the components listed in the table below were weighed in a container and mixed in a prism high-speed mixer for 30 seconds at 3500 RPM to form a dry homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19mm twin-screw extruder with an aggressive screw configuration and a speed of 500 RPM. The first zone was set at 30°C, and the second, third, and fourth zones were set at 110°C. The feed rate was such that a torque of 45-55% was observed on the equipment. Upon exiting the extruder, the mixtures were dropped onto a set of chill rolls to cool and re-solidify the mixtures into solid chips. The chips were weighed and 0.15% of Aerosil 200 was added before milling in a Mikro ACM®- 1 Air Classifying Mill to obtain a particle size of 5 to 90 microns with a majority of the particles being from 20 to 50 microns and an average particle size of approximately27-32 microns. The resulting coating compositions for each Example were solid particulate powder coating compositions that were free flowing.Table 58Preparation of powder coatings in gramsApplication

[0278] The cured powder coating compositions prepared above were applied with an Encore Nordson powder coating cup gun at 75kV, 15mA restricted, 10 psi atomizing and 10 psi conveying flow air. The coating thickness was between 64 pm to 83 pm for the single coat compositions. The coatings were cured 375°F for 20 minutes to form a single coating layer. Substrates coated are listed below with testing.Testing

[0279] Comparative corrosion examples were tested as per B117 ASTM salt spray corrosion with a scribe cut down to middle of a panel exposing metal on 4inX6in B1 17 corrosion test panels. Panel substrate and pretreatment types are listed with the corrosion results. After testing the panels were scraped free of lose coating and corrosion products under a warm water flow. The exposed metal andcorrosion product scribe creep was measured as total scribe creep across the exposed area 90° to the scribe line. An average of 5 readings on two panels was reported in millimeters total scribeTable 59500 Hours B117 Corrosion TestingTable 60750 Hours B117 Corrosion TestingTable 611000 Hours B1 17 Corrosion TestingTable 62Additional Testing B1000 P99X ACT substrate

[0280] The results show improved B117 salt spray scribe corrosion with the poly THF 650 isocyanate pre-polymer based epoxy functional oxazolidone versus an unmodified control. This approach utilizes epoxy functionality but with a modified structure based on poly THF isocyanate prepolymer structure.I. Preparation of coating compositions utilizing poly THF 250 based isocyanate prepolymers to make epoxy functional oxazolidone

[0281] Each of the components listed in the table below were weighed in a container and mixed in a prism high-speed mixer for 30 seconds at 3500 RPM toform a dry homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19mm twin-screw extruder with an aggressive screw configuration and a speed of 500 RPM. The first zone was set at 30°C, and the second, third, and fourth zones were set at 110°C. The feed rate was such that a torque of 45-55% was observed on the equipment. Upon exiting the extruder, the mixtures were dropped onto a set of chill rolls to cool and re-solidify the mixtures into solid chips. The chips were weighed and 0.15% of Aerosil 200 was added before milling in a Mikro ACM®- 1 Air Classifying Mill to obtain a particle size of 5 to 90 microns with a majority of the particles being from 20 to 50 microns and an average particle size of approximately 27-32 microns. The resulting coating compositions for each Example were solid particulate powder coating compositions that were free flowing.Table 63Preparation of powder coatings in gramApplication

[0282] The cured powder coating compositions prepared above were applied with an Encore Nordson powder coating cup gun at 75kV, 15mA restricted, 10 psi atomizing and 10 psi conveying flow air. The coating thickness was between 64 pm to 83 pm for the single coat compositions. The coatings were cured 375°F for 20 minutes to form a single coating layer. Substrates coated are listed below with testing.Testing

[0283] Comparative corrosion examples were tested as per B117 ASTM salt spray corrosion with a scribe cut down to middle of a panel exposing metal on 4inX6in B1 17 corrosion test panels. Panel substrate and pretreatment types are listed with the corrosion results. After testing the panels were scraped free of lose coating and corrosion products under a warm water flow. The exposed metal and corrosion product scribe creep was measured as total scribe creep across the exposed area 90° to the scribe line. An average of 5 readings on two panels was reported in millimeters total scribeTable 64500 Hours B117 Corrosion TestingTable 65500 Hours B117 Corrosion TestingTable 66Additional Testing B1000 P99X ACT substrate

[0284] The results show improved corrosion resistance with TGIC and Primid cured polyester powder compositions when modified with the poly THF250 IPDI prepolymer di-epoxy oxazolidone. We can see improved corrosion resistance with the longer chain 650 and shorter chain 250 versions of poly THF.J. Preparation of coating compositions utilizing poly THF 250 based isocyanates to make epoxy functional oxazolidone

[0285] Each of the components listed in the table below were weighed in a container and mixed in a prism high-speed mixer for 30 seconds at 3500 RPM to form a dry homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19mm twin-screw extruder with an aggressive screw configuration and a speed of 500 RPM. The first zone was set at 30°C, and the second, third, and fourth zones were set at 110°C. The feed rate was such that a torque of 45-55% was observed on the equipment. Upon exiting the extruder, the mixtures were dropped onto a set of chill rolls to cool and re-solidify the mixtures into solid chips. The chips were weighed and 0.15% of Aerosil 200 was added before milling in a Mikro ACM®- 1 Air Classifying Mill to obtain a particle size of 5 to 90 microns with a majority of the particles being from 20 to 50 microns and an average particle size of approximately 27-32 microns. The resulting coating compositions for each Example were solid particulate powder coating compositions that were free flowing.Table 67Preparation of powder coatings in gramsApplication

[0286] The cured powder coating compositions prepared above were applied with an Encore Nordson powder coating cup gun at 75kV, 15mA restricted, 10 psi atomizing and 10 psi conveying flow air. The coating thickness was between 64 pm to 83 pm for the single coat compositions. The coatings were cured 375°F for 20 minutes to form a single coating layer. Substrates coated are listed below with testing.Testing

[0287] Comparative corrosion examples were tested as per B117 ASTM salt spray corrosion with a scribe cut down to middle of a panel exposing metal on 4inX6in B1 17 corrosion test panels. Panel substrate and pretreatment types are listed with the corrosion results. After testing the panels were scraped free of lose coating and corrosion products under a warm water flow. The exposed metal and corrosion product scribe creep was measured as total scribe creep across the exposed area 90° to the scribe line. An average of 5 readings on two panels was reported in millimeters total scribeTable 68500 Hours B117 Corrosion TestingTable 69336 Hours B117 Corrosion TestingTable 701200 Hours B1 17 Corrosion TestingTable 71Additional Testing B1000 P99X ACT substrate

[0288] The results show improved B117 salt spray scribe corrosion with the TGIC and Primid cured polyester powder compositions when modified with poly THF250 IPDI pre-polymer di-epoxy oxazolidone oligomer.K. Preparation of Coating Compositions utilizing an acid functional oxazolidone and poly THF based oxazolidone

[0289] Each of the components listed in the table below were weighed in a container and mixed in a prism high-speed mixer for 30 seconds at 3500 RPM to form a dry homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19mm twin-screw extruder with an aggressive screw configuration and a speed of 500 RPM. The first zone was set at 30°C, and the second, third, and fourth zones were set at 110°C. The feed rate was such that a torque of 45-55% was observed on the equipment. Upon exiting the extruder, the mixtures were dropped onto a set of chill rolls to cool and re-solidify the mixtures into solid chips. The chips were weighed and 0.15% of Aerosil 200 was added before milling in a Mikro ACM®- 1 Air Classifying Mill to obtain a particle size of 5 to 90 microns with a majority of the particles being from 20 to 50 microns and an average particle size of approximately 27-32 microns. The resulting coating compositions for each Example were solid particulate powder coating compositions that were free flowing.Table 72Preparation of powder coatings in gramsApplication

[0290] The cured powder coating compositions prepared above were applied with an Encore Nordson powder coating cup gun at 75kV, 15mA restricted, 10 psi atomizing and 10 psi conveying flow air. The coating thickness was between 64 pm to 83 pm for the single coat compositions. The coatings were cured 375°F for 20 minutes in an electric oven to form a coating layer.Testing

[0291] Comparative corrosion examples were tested as per B117 ASTM salt spray corrosion with a scribe cut down to middle of a panel exposing metal on 4inX6in test panels. Panel substrate and pretreatment types are listed with the corrosion results. After testing, the panels were scraped free of lose coating and corrosion products under a warm water flow. The exposed metal and corrosion product scribe creep was measured as total scribe creep across the exposed area 90° to the scribe line. An average of 5 readings on two panels was reported in millimeters total scribe creep is reported in the tables below.Table 731000 Hours B1 17 Corrosion TestingTable 74500 Hours B117 Corrosion Testing

[0292] In a primid cured polyester powder composition there is improved corrosion resistance with a poly THF650 based isocyanate oxazolidone di-epoxy modification and an acid functional oxazolidone modification. Acid functional oxazolidones can be utilized to improve corrosion resistance.L. Preparation of Coating Compositions utilizing an acid functional oxazolidone

[0293] Each of the components listed in the table below were weighed in a container and mixed in a prism high-speed mixer for 30 seconds at 3500 RPM to form a dry homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19mm twin-screw extruder with an aggressive screw configuration and a speed of 500 RPM. The first zone was set at 30°C, and the second, third, and fourth zones were set at 110°C. The feed rate was such that a torque of 45-55% was observed on the equipment. Upon exiting the extruder, the mixtures were dropped onto a set of chill rolls to cool and re-solidify the mixtures into solid chips. The chips were weighed and 0.15% of Aerosil 200 was added before milling in a Mikro ACM®- 1 Air Classifying Mill to obtain a particle size of 5 to 90 microns with a majority of the particles being from 20 to 50 microns and an average particle size of approximately 27-32 microns. The resulting coating compositions for each Example were solid particulate powder coating compositions that were free flowing.Table 75Preparation of powder coatings in gramsc TOTAL| 100 | 1001Application

[0294] The cured powder coating compositions prepared above were applied with an Encore Nordson powder coating cup gun at 75kV, 15mA restricted, 10 psi atomizing and 10 psi conveying flow air. The coating thickness was between 64 pm to 83 pm for the single coat compositions. The coatings were cured 350°F for 20 minutes in an electric oven to form a coating layer.Testing

[0295] Comparative corrosion examples were tested as per B117 ASTM salt spray corrosion with a scribe cut down to middle of a panel exposing metal on 4inX6in test panels. Panel substrate types and pretreatments are listed with the corrosion results. After testing, the panels were scraped free of lose coating and corrosion products under a warm water flow. The exposed metal and corrosion product scribe creep was measured as total scribe creep across the exposed area 90° to the scribe line. An average of 5 readings on two panels was reported in millimeters total scribe creep is reported in the tables below.Table 76500 Hours B117 Corrosion TestingTable 77744 Hours B117 Corrosion TestingTable 781200 Hours B1 17 Corrosion Testing

[0296] The results show that an acid functional polyester oxazolidone can improve corrosion resistance against the non-modified comparable in a single coat application.M. Preparation of Coating Compositions utilizing poly THF 650 to prepare an isocyanate prepolymer based oxazolidone with epoxy functionality reacted with a mono-acid

[0297] Each of the components listed in the table below were weighed in a container and mixed in a prism high-speed mixer for 30 seconds at 3500 RPM to form a dry homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19mm twin-screw extruder with an aggressive screw configuration and a speed of 500 RPM. The first zone was set at 30°C, and the second, third, and fourth zones were set at 110°C. The feed rate was such that a torque of 45-55% was observed on the equipment. Upon exiting the extruder, the mixtures were dropped onto a set of chill rolls to cool and re-solidify the mixtures into solid chips. The chips were weighed and 0.15% of Aerosil 200 was added before milling in a Mikro ACM®- 1 Air Classifying Mill to obtain a particle size of 5 to 90 microns with a majority of the particles being from 20 to 50 microns and an average particle size of approximately 27-32 microns. The resulting coating compositions for each Example were solid particulate powder coating compositions that were free flowingTable 79Preparation of powder coatings in gramsTesting

[0298] Comparative corrosion examples were tested as per B117 ASTM salt spray corrosion with a scribe cut down to middle of a panel exposing metal on 4inX6in test panels. Panel substrate and pretreatment types are listed with the corrosion results. After testing, the panels were scraped free of lose coating and corrosion products under a warm water flow. The exposed metal and corrosion product scribe creep was measured as total scribe creep across the exposed area 90° to the scribe line. An average of 5 readings on two panels was reported in millimeters total scribe creep is reported in the tables below.Table 801000 Hours B1 17 Corrosion TestingTable 811000 Hours B1 17 Corrosion TestingTable 821800 Hours B1 17 Corrosion Testing

[0299] The results show improved corrosion performance with a poly THF 650 isocyanate prepolymer di-epoxy oxazolidone with the epoxy groups reacted off with a mono-acid.N. Preparation of Coating Compositions utilizing oxazolidones prepared with a poly THF, IPDI prepolymer with the terminal epoxy group capped with nonanoic acid and the ring opened hydroxyl reacted with a mono-isocyanate.

[0300] Each of the components listed in the table below were weighed in a container and mixed in a prism high-speed mixer for 30 seconds at 3500 RPM toform a dry homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19mm twin-screw extruder with an aggressive screw configuration and a speed of 500 RPM. The first zone was set at 30°C, and the second, third, and fourth zones were set at 110°C. The feed rate was such that a torque of 45-55% was observed on the equipment. Upon exiting the extruder, the mixtures were dropped onto a set of chill rolls to cool and re-solidify the mixtures into solid chips. The chips were weighed and 0.15% of Aerosil 200 was added before milling in a Mikro ACM®- 1 Air Classifying Mill to obtain a particle size of 5 to 90 microns with a majority of the particles being from 20 to 50 microns and an average particle size of approximately 27-32 microns. The resulting coating compositions for each Example were solid particulate powder coating compositions that were free flowing.Table 82APreparation of powder coatings in gramsApplication

[0301] The cured powder coating compositions prepared above were applied with an Encore Nordson powder coating cup gun at 75kV, 15mA restriction, 10 psi atomizing and 10 psi conveying flow air. The coating thickness was between 64um to 83um for the single coat compositions. The coatings were cured 375°F for 20 minutes to form a single coating layer. Substrates coated are listed below with testing.Testing

[0302] Comparative corrosion examples were tested as per B117 ASTM salt spray corrosion with a scribe cut down to middle of a panel exposing metal on4inX6in B1 17 corrosion test panels. Panel substrate and pretreatment types are listed with the corrosion results. After testing the panels were scraped free of loose coating and corrosion products under a warm water flow. The exposed metal and corrosion product scribe creep was measured as total scribe creep across the exposed area 90° to the scribe line. An average of 5 readings per panel for B117 panels.Table 82B1008 Hours B1 17 Corrosion TestingTable 82C768 Hours B117 Corrosion TestingConclusion

[0303] The results indicate improved B117 salt spray scribe corrosion with the oxazolidone resin prepared with a poly THF, IPDI prepolymer with the terminal epoxy group capped with nonanoic acid and the ring opened hydroxyl reacted with a monoisocyanate versus an unmodified control.IV. Liquid Coating Compositions ExamplesA. Preparation of Liquid Coating Compositions utilizing THF 250 based oxazolidone

[0304] Each of the components listed in the table below were weighed in a container and mixed under high shear using a Cowles blade for 20 minutes to form a homogeneous mixture. The mixture was then milled in a horizontal ball mill (Eiger mill, M250VSEEXP) for 60 minutes at 3000 RPM using 0.8 - 1 .2 mm zirconia beads. The mill was water-cooled for the duration of milling. The fineness of grind of the milled composition was verified as 6.0 on a Hegman gauge.Table 83Preparation of liquid coatings in grams

[0305] In the composition listed in the table above, the methyl amyl ketone was added after milling as a mill wash

[0306] After milling, the components listed in the table below were mixed into the milled composition using a low shear mixing blade for 20 minutes.Table 84Formulations in Example A-EApplication

[0307] The liquid coating compositions prepared above were applied with a 3M Accuspray HG14 spray gun at 25 psi atomizing air pressure. The coating thickness was between 65um to 85um. The coatings were cured 180°F for 20 minutes after a 10-minute flash-off period to form a single coating layer. Substrates coated are listed below with testing.Testing

[0308] Comparative corrosion examples were tested as per B117 ASTM salt spray corrosion with a scribe cut down the middle of a panel exposing metal on 4inX6in B1 17 corrosion test. Panel substrate types are listed with the corrosion results. After testing the panels were scraped free of lose coating and corrosion products under a warm water flow. The exposed metal and corrosion product scribe creep was measured as total scribe creep across the exposed area 90° to the scribe line. An average of 8 readings on two panels was reported in millimeters total scribe creep average is reported in the tables below.Table 85500 Hours B117 Corrosion Testing

[0309] The adhesion of the composition to untreated, cold-rolled steel substrates was characterized according to the standard test method ASTM D3359- 22 tape adhesion test. This method quantifies adhesion based on the fraction of material removed with ratings from 0 to 5, 5 representing perfect adhesion.Table 86Dry adhesion testing

[0310] The results show improved B117 salt spray scribe corrosion and dry adhesion in liquid coatings when the THF-250 based oxazolidone resin is added to the formulation in the letdown stage.B. Preparation of Liquid Coating Compositions utilizing TSR-400 based oxazolidone

[0311] Each of the components listed in the table below were weighed in a container and mixed under high shear using a Cowles blade for 20 minutes to form a homogeneous mixture. The mixture was then milled in a horizontal ball mill (Eiger mill, M250VSEEXP) for 60 minutes at 3000 RPM using 0.8 - 1 .2 mm zirconia beads. The mill was water-cooled for the duration of milling. The fineness of grind of the milled composition was verified as 6.0 on a Hegman gauge.Table 87Preparation of liquid coatings in grams

[0312] In the composition listed in the table above, the methyl amyl ketone was added after milling as a mill wash

[0313] After milling, the components listed in the table below were mixed into the milled composition using a low shear mixing blade for 20 minutes.Table 88Formulations in Examples L6-L8Application

[0314] The liquid coating compositions prepared above were applied with a 3M Accuspray HG14 spray gun at 25 psi atomizing air pressure. The coating thickness was between 65um to 85um. The coatings were cured 180°F for 20 minutes after a 10-minute flash-off period to form a single coating layer. Substrates coated are listed below with testing.Testing

[0315] Comparative corrosion examples were tested as per B117 ASTM salt spray corrosion with a scribe cut down the middle of a panel exposing metal on 4inX6in B1 17 corrosion test. Panel substrate types are listed with the corrosion results. After testing the panels were scraped free of lose coating and corrosion products under a warm water flow. The exposed metal and corrosion product scribe creep was measured as total scribe creep across the exposed area 90° to the scribe line. An average of 8 readings on two panels was reported in millimeters total scribe creep average is reported in the tables below.Table 89500 Hours B117 Corrosion Testing

[0316] The adhesion of the composition to untreated, cold-rolled steel substrates was characterized according to the standard test method ASTM D3359- 22 tape adhesion test. This method quantifies adhesion based on the fraction of material removed with ratings from 0 to 5, 5 representing perfect adhesion.Table 90Dry adhesion testing

[0317] The results show improved B117 salt spray scribe corrosion and dry adhesion in liquid coatings when the THF-250 based oxazolidone resin is added to the formulation in the letdown stage.C. Preparation of Liquid Coating Compositions utilizing IPDI+ Eponex 1520 based oxazolidone

[0318] Each of the components listed in the table below were weighed in a container and mixed under high shear using a Cowles blade for 20 minutes to form a homogeneous mixture. The mixture was then milled in a horizontal ball mill (Eigermill, M250VSEEXP) for 60 minutes at 3000 RPM using 0.8 - 1 .2 mm zirconia beads.The mill was water-cooled for the duration of milling. The fineness of grind of the milled composition was verified as 6.0 on a Hegman gauge.Table 91Preparation of liquid coatings in grams

[0319] In the composition listed in the table above, the methyl amyl ketone was added after milling as a mill wash.

[0320] After milling, the components listed in the table below were mixed into the milled composition using a low shear mixing blade for 20 minutes.Table 92Formulations of Examples A-DApplication

[0321] The liquid coating compositions prepared above were applied with a 3M Accuspray HG14 spray gun at 25 psi atomizing air pressure. The coating thickness was between 65um to 85um. The coatings were cured 180°F for 20minutes after a 10-minute flash-off period to form a single coating layer. Substrates coated are listed below with testing.Testing

[0322] Comparative corrosion examples were tested as per B117 ASTM salt spray corrosion with a scribe cut down the middle of a panel exposing metal on 4inX6in B1 17 corrosion test. Panel substrate types are listed with the corrosion results. After testing the panels were scraped free of lose coating and corrosion products under a warm water flow. The exposed metal and corrosion product scribe creep was measured as total scribe creep across the exposed area 90° to the scribe line. An average of 8 readings on two panels was reported in millimeters total scribe creep average is reported in the tables below.Table 93500 Hours B117 Corrosion Testing

[0323] The results show improved B117 salt spray scribe corrosion in liquid coatings when the IPDI + Eponex 1510 based oxazolidone resin is added to the formulation in the letdown stage.V. Packaging Coating Compositions ExamplesMaterials and Methods

[0324] The following definitions and methods were used for the packaging coating examples.

[0325] Acid Value / Acid Number: determined by titration with 0.1 M methanolic potassium hydroxide (KOH) solution. Acid Value is sometimes abbreviated as AV.

[0326] Hydroxyl Value (OHV): measured as the number of mg of KOH equivalent to the hydroxy groups in 1g of material

[0327] Molecular Weight (Mn): number average determined by gel permeation chromatography using a polystyrene standard according to ASTM D6579-11.

[0328] Viscosity measurement of the aqueous dispersions were measured using a Brookfield viscometer (RV series) using a #4 spindle at 50 rpms and 25°C.

[0329] MEK rubs: The coatings were evaluated for the number of double rubs by hand it took to soften and break through the coating with a rag saturated with methyl ethyl ketone.

[0330] Blush: Coatings were evaluated for their ability of a coating to resist attack by various test solutions. When the coated film absorbs the test solution, it generally becomes cloudy or looks white. Blush is measured visually using a scale of 1 to 10 where a rating of “10” indicates no blush and a rating of “0” indicates complete whitening of the film. Blush ratings of at least 7 are typically desired for commercially viable coatings. Coated panels are cut into 2 inch by 4 inch pieces and half immersed into the test solution.

[0331] Adhesion: The adhesion test was performed according to ASTM D 3359 Test Method B, using Scotch 610 tape, available from 3M Company of Saint Paul, Minn. Adhesion is generally rated on a scale of 0 to 5 where a rating of “5” indicates no adhesion failure.

[0332] Acetic Acid: The Acetic Acid test is designed to measure the resistance of a coating to a boiling 3% acetic acid solution. The solution is prepared by mixing 90 grams of Glacial Acetic Acid (product of Fisher Scientific) into 3000 grams of deionized water. Coated strips are immersed into the boiling Acetic Acid solution for 30 minutes. The strips are then rinsed and cooled in deionized water, dried, and immediately rated for blush and adhesion as described previously.

[0333] Dowfax: The Dowfax test is designed to measure the resistance of a coating to a boiling detergent solution. The solution is prepared by mixing 5 grams of DOWFAX 2A1 (product of Dow Chemical) into 3000 grams of deionized water. Coated strips are immersed into the boiling Dowfax solution for 15 minutes. The strips are then rinsed and cooled in deionized water, dried, and immediately rated for blush and adhesion as described previously.

[0334] Joy: The Joy test is designed to measure the resistance of a coating to a hot 180°F (82°C) Joy detergent solution. The solution is prepared by mixing 30grains of Ultra Joy Dishwashing Liquid (product of Procter & Gamble) into 3000 grams of deionized water. Coated strips are immersed into the 180° F. (82°C.) Joy solution for 15 minutes. The strips are then rinsed and cooled in deionized water, dried, and immediately rated for blush and adhesion as described previously.

[0335] Water Retort: The DI Water Retort test is designed to measure the resistance of a coating to deionized water steam. Coated strips are immersed into the deionized water and placed in a steam retort for 30 minutes at 250°F (121 °C). The strips are then cooled in deionized water, dried, and immediately rated for blush and adhesion as described previously.

[0336] Wedge Bend: Flexibility of the coatings was evaluated using a wedge bend test. Coated panels were cut into 2 inch by 4 inch pieces, with the substrate grain running perpendicular to the long length of the cut panel. They were then bent over a 1 / 8 inch metal rod along the long length of the panel with the coated side facing out. Bent coupons were then placed onto a block of metal where a wedge was pre-cut out of it with a taper of 0 to 1 / 8 inch along a 4 inch length. Once placed in the wedge, each bent coupon was struck with a block of metal which weighed 4 pounds from a height of 12 inches to form a wedge where one end of the coated metal impinged upon itself and a 1 / 8 inch space remained on the opposite end. Wedge bent panels were then placed into an aqueous solution of copper sulfate and hydrochloric acid containing 1020 grams DI Water, 380 grams 6N hydrochloric acid, and 400 grams copper sulfate. The panels were held in the aqueous solution for one minute to purposely etch the aluminum panel in areas where the coatings failed and cracked. The etched wedge bent panels were then examined through a microscope at 10x power to determine how far from the impinged end along the bent radii did the coating crack. Flexibility results are reported as either the length of cracked area from the impinged end or the percentage of cracked area versus total length of the wedge bent panel.

[0337] Hot Feathering: The panel was then cut into a 50.8 mm by 88.9 mm piece, with the substrate grain running perpendicular to the long length of the cut panel. The test panel coated side up was then inserted between the score tool and the anvil in a Carver press. The long edge of the panel was abutted against the guide block on the inside of the press. The valve on the base of the press was tightened to clamp the panel into the Carver press. A force of 1500 psi on thehydraulic pressure gauge was applied to make the score line of a simulated tab. The depth of the score line was 0.18 mm.

[0338] The schematic above shows the coated panel (100) comprising the score line of the simulated tab (102). The simulated tab (102) extended perpendicularly to the long length (I) of the panel. The terminal points (104, 106) of the score line (which collectively form the front of the simulated tab, i.e. the portion of the tab that was first opened) were both arranged at an edge of the long length (I) of the panel. The dimensions of the simulated tab (102) were: A (48.0 mm); B (11 .3 mm); C (24.0 mm); D (18.00 mm); E and F area (89.4 mm'), and G (10.6 mm). Lengths D extended from the upper terminal point of respective length C to the left and right vertex of circles E and F, respectively. Length G extended between the upper vertex of circles E and F. The panel was then removed from the press and two spaced parallel cuts were formed in the panel at the front end of the simulated tab along the score line. Each cut extended inward into the panel, perpendicularly to the long length, starting from the terminal points (104 and 106) of the score line. The cuts extended 6.4 mm into the panel along the respective portion of the score lineand were spaced 11 .3 mm apart. The panel was then fully immerged into deionized water for 10 minutes at 212°F (100°C). The panel was then removed and immediately submerged in 22°C deionized water for 2 seconds. The panel was then removed from the deionized water. The cut portion of the simulated tab was bent 180° toward the coated face of the panel. The panel was then inserted into a vice where the panel was held along the long length, with the edge from which the score line extended being held in the vice. Pliers were then used to grip the cut portion of the simulated tab and then to pull the cut portion of the tab 180° across the coated face of the panel toward the opposite end of the tab at a rate of 1 second / cm. Feathering was then measured using a digital Microscope. The length of the coating that extended furthest into the tab opening was measured in mm and recorded.A. Polyester Acrylic Resin

[0339] Polyester 1 : The diol, diacid and catalyst listed in Table 92 were added as a batch to a vessel with a steam column, distillation head and condenser. The batch temperature was increased to 180°C with continuous stirring at 400 rpms and a nitrogen gas blanket at 0.5 SCFH. Then the batch temperature was increased to 230°C in 10°C steps each hour over a 4-hour period. The temperature of the vapor was monitored continuously, and the batch temperature was not raised for each step until the vapor temperature had dropped below 80°C.

[0340] Once the reaction temperature had reached 230°C the acid value (AV) of the polymer was checked every hour until AV dropped below a value of 20. Prior to that if the resin became clear the N2 blanket was switched to a 0.5 SCFH sparge. Once at an AV less than 20 the sparge was switched back to a blanket and the reaction was cooled to 150°C.

[0341] The mequinol (MeHQ) was then added, followed by the maleic anhydride 10 minutes later. The reaction temperature was raised to 220°C, sparge re-applied, and monitored by manual sampling of the resin and analysis by AV measurements every couple of hours. Once the acid value had dropped below 20 the reaction was cooled to 130°C, then xylene was added by an addition funnel under a nitrogen blanket of 0.5 SCFH. After the xylene had been added the reaction overheads were switched to an azeotropic distillation setup with extra xylene addedto the attached Dean-Stark trap. The reaction was heated up again to 220°C and a 0.5 SCFH nitrogen gas sparge was re-applied to the reaction.

[0342] The reaction was monitored by AV by acquiring samples of the xylene- containing resin and reducing the solids of that material to a % solids that would allow for a comparison against standardized bubble tube references (references supplied by Gardco and all bubble tube samples cooled to 25°C before analysis). This "cut-viscosity" was used to assess the extent of the polymerization and a bubble tube viscosity of Z4-Z5 at 55% solids was defined as the primary target. An acid value below 10 was assigned as the secondary target. Once the cut-viscosity had been achieved the reaction was sampled for hydroxyl value content.

[0343] The resin was cooled to 130°C and Dowanol DPM solvent was added. After 1 hour the final solvated material was poured out and analyzed for its acid value and molecular weight.Table 94Polyester Prepared in Study

[0344] PGA resin 1 : The acrylic modified polyester was formed as follows. The mass of Polyester 1 in the amount specified in Table 94 was added to a round- bottomed flask and enough Dowanol DPM was added to reduce the theoreticalsolids to 59%. The material was heated to 130°C under continuous stirring at 400 rpms under a 0.5 SCFH nitrogen gas blanket.

[0345] The methacrylic monomers shown in Table 95 were pre-mixed and then added over a 40 min period. After 10 minutes 87 wt.% of initiator shown in Table 95 was diluted with three times the mass of Dowanol DPM. This resulting mixture was then added over a 30-minute period. Both the monomer and initiator separate feeds ended at the same time. Following this the reaction was held at 130°C for 60 min. Next 13 wt.% of initiator shown in Table 95 was diluted with three times the mass of Dowanol DPM. The resulting mixture was then added to the reaction over a 5-minute period. Small amounts of Dowanol DPM were added to the monomer and initiator funnels and that volume of liquid was drained into the reaction. The reaction was then held at 130°C for 120 minutes. After the hold the polyester-grafted-acrylic (PGA) resin was poured out and analyzed for acid value (AV) and molecular weight.Table 95Solventborne Polyester-graft-acrylic (PGA) Resin

[0346] Aqueous Dispersion 1 : The PGA Resin 1 was formed into an aqueous dispersion by heating the resin to 90°C and adding dimethylethanolamine withcontinuous stirring at 400 rpm and a 0.5 SCFH nitrogen gas blanket. The mixture was allowed to stir for 10 minutes, then deionized water that had been pre-heated to 60°C was added over a 30-minute period making sure to keep the reaction temperature above 85°C. The aqueous dispersion was allowed to cool to 45°C before being filtered through a 5 pm filter bag. The aqueous dispersion was analyzed for solids and viscosity.Table 96Aqueous DispersionsB. Oxazolidone Resin

[0347] Oxazolidone Resin 1 : The oxazolidone modified resin was formed as follows. To a 1000 mL, 4-necked flask equipped with a motor driven stainless steel stir blade, a water-cooled condenser, a nitrogen blanket, and a heating mantle with a thermometer connected through a temperature feedback control device, 202.3 grams of Eponex 1510 (commercially available from Hexion Specialty Chemicals) and 0.72 grams of tetrabutylphosphonium bromide (Commercially available from Sigma Aldrich) were added. The reaction mixture was heated to 170 to 175°C. 50 grams of isophorone diisocyanate ( I PD I , commercially available from Covestro LLC)) was added into reaction mixture dropwise for 1 hour. After addition, the reaction mixture was held at 170 to 180°C until IR spectroscopy showed the absence of the characteristic NCO band (2269 cm-1 ) using the Thermo Scientific Nicolet iS5 FT-IR. Then, the reaction mixture was cooled to 120°C and 200 grams of Dowanol DPM (commercially available from Dow) was added into reaction mixture. The obtained resin was poured out from flask at 80°C. The solid of this resin is 57%. The weight average molecular weight was 9406 g / mol as determined by gel permeation chromatography (GPC). GPC was performed using a Waters 2695 separation module with a Waters 410 differential refractometer (Rl detector) and polystyrenestandards. The molecular weight (Mw or Mn) values reported herein were determined using this method. Tetrahydrofuran (THF) was used as the eluent at a flow rate of 1 mL min, and two PL Gel Mixed C columns were used for separation.

[0348] Coating formulations: Examples PKG3 to PKG6 were prepared by combining all of the materials under mixing for 15 minutes with a mixing blade. Coated panels were obtained by drawing paints over 0.0080” Bonderite 702 chrome pretreated aluminum panels (AA5182 Alloy) using a wire wound rod to obtain dry coating weight of approximately 6.5 to 7.0 mg / square inch (msi). Coated panels were then immediately placed into a one-zone, gas-fired, conveyor oven for 12 seconds and baked to a peak metal temperature of 465 °F (240.5°C).Table 97Coating FormulationsTable 98Cured Coating PropertiesTable 99Hot Feathering for Examples 1 -4ASPECTS

[0349] Aspect 1 is a method for synthesizing an oxazolidone compound according to Formula (I):

[0350] wherein R is a connective group comprising a polyether, polyester, polyurethane, alkyl, or aromatic functional group; Ri is a terminal group comprising an epoxy, acid, hydroxyl, or amine containing group, or a non-functional group; R2 is a connective group comprising an aromatic functional group or an aliphatic functional group; and n is from 1 to 500; the method comprising: (i) reacting an isocyanate compound and an epoxy compound in the presence of a catalyst to produce an intermediate compound comprising at least two oxazolidone functional groups linked by R and comprising linking groups R2; and (ii) reacting the intermediate compound with a further compound to provide R1 end groups to produce the oxazolidone compound according to Formula (I).

[0351] Aspect 2 is the method of Aspect 1 , wherein the isocyanate compound is a diiosocyanate.

[0352] Aspect 3 is the method of Aspect 1 , wherein the isocyanate compound is an isocyanate pre-polymer prepared by reacting a polyisocyanate with a polyol in the presence of a urethane catalyst.

[0353] Aspect 4 is the method of Aspect 3, wherein the polyol is polytetrahydrofuran and the urethane catalyst is dibutylin dilaurate.

[0354] Aspect 5 is the method of any one of Aspects 1 to 4, wherein the epoxy compound is an aliphatic epoxy compound.

[0355] Aspect 6 is the method of any one of Aspects 1 to 4, wherein the epoxy compound is an aromatic epoxy compound.

[0356] Aspect 7 is the method of any one of Aspects 1 to 6, wherein step (i) is conducted at a temperature of from 100°C to 180°C.

[0357] Aspect 8 is the method of any one of Aspects 1 to 7, wherein the catalyst is present in an amount of from 20 ppm to 5000 ppm, based on the total weight of the isocyanate compound and the epoxy compound.

[0358] Aspect 9 a composition comprising an oxazolidone functional compound according to Formula (I):

[0359] wherein R is a connective group comprising a polyether, polyester, polyurethane, alkyl, or aromatic functional group; Ri is a terminal group comprising an epoxy, acid, hydroxyl, or amine containing group, or a non-functional group; R2 is a connective group comprising an aromatic functional group or an aliphatic functional group; and n is from 1 to 500; and a solvent medium.

[0360] Aspect 10 is the composition of Aspect 9, wherein R comprises is a tolyl group.

[0361] Aspect 11 is the composition of Aspect 9, wherein R comprises a phenyl group.

[0362] Aspect 12 is the composition of Aspect 9, wherein R comprises a 1 ,1 ,3, -trimethylcyclohexane group.

[0363] Aspect 13 is the composition of Aspect 9, wherein R comprises a 4,4’- (propane-2,2-diyl)bis(methoxybenzene) group.

[0364] Aspect 14 is the composition of Aspect 9, wherein Ri comprises an amine group, and the composition is free from epoxy groups.

[0365] Aspect 15 is the composition of Aspect 9, wherein R comprises a tolyl or phenyl group and Ri is an epoxy group.

[0366] Aspect 16 is the composition of any of Aspects 9 to 15, wherein the at least two oxazolidone functionalities are present in an amount of from 1 wt.% to 10 wt.%, based on a total weight of the compound.

[0367] Aspect 17 is the composition of any of Aspects 9 to 16, wherein R2 is an aliphatic group.

[0368] Aspect 18 is the composition of any of Aspects 9 to 17, wherein the compound according to Formula (I) has a weight / number average molecular weight from 400 to 10,000.

[0369] Aspect 19 is an electrocoat composition comprising: a cationic film forming resin; and an additive compound comprising at least two oxazolidone functionalities, wherein the additive compound has two terminal groups each comprising an amine group, and the additive compound is free of epoxy groups.

[0370] Aspect 20 is the composition of Aspect 19, wherein the additive compound further comprises: at least two connective groups, comprising, and independently selected from, at least one of an aromatic group and an aliphatic group.

[0371] Aspect 21 is the composition of Aspect 20, wherein connective groups are derived from bisphenol A.

[0372] Aspect 22 is the composition of any one of Aspects 19 to 21 , wherein the film forming resin comprises an acrylic resin, an epoxy resin, or a combination of the foregoing.

[0373] Aspect 23 is the composition of any one of Aspects 19 to 22, further comprising a blocked isocyanate crosslinking agent.

[0374] Aspect 24 is the composition of Aspect 23, wherein the crosslinking agent is present in an amount from 25 wt.% to 55 wt.%, based on a total weight of the composition.

[0375] Aspect 25 is the composition of any one of Aspects 19 to 24, wherein the amine group is derived from diethylenetriamine or N-methylethanol amine.

[0376] Aspect 26 is the composition of any one of Aspects 19 to 25 wherein the additive compound is present in an amount of from 4 wt.% to 10 wt.%, based on a total weight of the composition.

[0377] Aspect 27 is the composition of any one of Aspects 19 to 26, wherein the film forming resin is present in an amount of from 50 wt.% to 90 wt.%, based on a total weight of the composition.

[0378] Aspect 28 is the composition of any one of Aspects 19 to 27, wherein subsequent to curing to form a coating, the oxazolidone groups equivalents per coating weight is from 100 g / equivalent wt. to 1 ,500 g / equivalent wt.

[0379] Aspect 29 is an article coated with a coating comprising a cured form of the coating composition of any one of Aspects 19 to 28.

[0380] Aspect 30 is the coated article of Aspect 29, wherein the coating demonstrates less than 10% scribe creep according to ASTM B117-19.

[0381] Aspect 31 is the coated article of Aspect 29 or 30, wherein the coating demonstrates a ranking of 4B or higher in the cross-hatch adhesion test according to ASTM D3359-22.

[0382] Aspect 32 is a powder coating composition comprising: a film forming resin; and an additive compound comprising at least two oxazolidone functionalities separated by a linking group, wherein the linking group is an aromatic functional group.

[0383] Aspect 33 is the composition of Aspect 32, wherein the additive compound further comprises: at least two connective groups, comprising, and independently selected from, at least one of an aromatic group and an aliphatic group; and optionally one or two terminal groups comprising an epoxy group.

[0384] Aspect 34 is the composition of Aspect 32 or 33, wherein the film forming resin is a polyester-acid resin.

[0385] Aspect 35 is the composition of any one of Aspects 32 to 34, wherein the film forming resin is a polyester-hydroxyl resin.

[0386] Aspect 36 is the composition of any one of Aspects 32 to 35, wherein the film forming resin is an epoxy resin.

[0387] Aspect 37 is the composition of any one of Aspects 32 to 36, wherein the film forming resin is an acrylic resin.

[0388] Aspect 38 is the composition of any one of Aspects 32 to 37, wherein the additive compound further comprises a poly-THF backbone.

[0389] Aspect 39 is the composition of any one of Aspects 32 to 38, further comprising a beta-hydroxyalkyl-amide crosslinking agent.

[0390] Aspect 40 is the composition of any one of Aspects 32 to 39, further comprising a triglycidyl isocyanurate cross-linking agent.

[0391] Aspect 41 is the composition of any one of Aspects 32 to 40, further comprising a blocked isocyanate cross-linker.

[0392] Aspect 42 is the composition of any one of Aspects 32 to 41 , further comprising a phenolic-based crosslinking agent.

[0393] Aspect 43 is the composition of any one of Aspects 32 to 42, wherein the connective groups are derived from bisphenol A.

[0394] Aspect 44 is the composition of any one of Aspects 32 to 43, wherein the additive compound is present in an amount from 1 wt.% to 30 wt.% based on a total weight of the composition.

[0395] Aspect 45 is an article coated with a coating comprising a cured form of the coating composition of any one of Aspects 32 to 44.

[0396] Aspect 46 is the coated article of Aspect 45, wherein the coating demonstrates less than 10% scribe creep according to ASTM B117-19.

[0397] Aspect 47 is the coated article of any Aspect 45 or 46, wherein the coating demonstrates a thermal conductivity of 0.3 W / m K or higher as measured according to ASTM D7984.

[0398] Aspect 48 is a a liquid coating composition, comprising: a polyester resin; and an additive compound comprising two oxazolidone functionalities and at least two terminal groups comprising, and independently selected from, at least one of, an epoxy group, an acid group, a hydroxyl group, an amine group, an aromatic group, and an aliphatic group.

[0399] Aspect 49 is the composition of Aspect 48, wherein the additive compound further comprises: at least two connective groups, comprising, and independently selected from, at least one of an aromatic group and an aliphatic group; and the at least two terminal groups of Aspect 48 comprise a hydroxyl functional aromatic group.

[0400] Aspect 50 is the composition of Aspect 48 or 49, wherein the film forming resin is a polyester resin.

[0401] Aspect 51 is the composition of any one of Aspects 48 to 50, further comprising an isocyanate crosslinking agent.

[0402] Aspect 52 is the composition of any one of Aspects 48 to 51 wherein the connective groups are derived from bisphenol A.

[0403] Aspect 53 is the composition of any one of Aspects 48 to 52, further comprising a pigment in the amount from 5 wt.% to 40 wt.%, based on a total weight of the composition.

[0404] Aspect 54 is the composition of any one of Aspects 48 to 53, further comprising a solvent in the amount from 5 wt.% to 40 wt.%, based on a total weight of the composition.

[0405] Aspect 55 is the composition of any one of Aspects 48 to 54, wherein the additive compound is present in an amount from 2 wt.% to 10 wt.%, based on a total weight of the coating composition.

[0406] Aspect 56 is the composition of any one of Aspects 48 to 55, wherein the -OH equivalent weight (EW) of the additive is from 300 to 1200, based on the resin solid.

[0407] Aspect 57 is an article coated with a coating comprising a cured form of the coating composition of any one of Aspects 48 to 56.

[0408] Aspect 58 is the coated article of Aspect 57, wherein the coating demonstrates a reduction in scribe creep of at least 10% according to ASTM B117- 19 compared to an article coated with the same oxazolidone-free coating.

[0409] Aspect 59 is a packaging coating composition comprising: a film forming resin comprising a polyester resin, an acrylic modified polyester, an acrylic resin or a combination thereof; and an additive compound comprising: at least two oxazolidone functionalities; at least two connective groups comprising an aliphatic group; and two terminal groups comprising an epoxy group.

[0410] Aspect 60 is the composition of Aspect 59, further comprising a benzoguanamine, blocked isocyanate, or phenolic crosslinking agent.

[0411] Aspect 61 is the composition of Aspect 59 or Aspect 60, wherein the additive compound is present in an amount from 1 wt.% to 5 wt.% based on the total resin solids of the coating composition.

[0412] Aspect 62 is the composition of Aspect 60 or Aspect 61 , wherein the crosslinking agent is present in an amount from 5 wt.% to 20 wt.%, based on the total resin solids of the coating composition.

[0413] Aspect 63 is the composition of any one of Aspects 59 to 63, wherein the film forming resin is present in an amount from 50 wt.% to 95 wt.%, based on the total resin solids of the coating composition.

[0414] Aspect 64 is an article coated with a coating comprising a cured form of the coating composition of any one of Aspects 59 to 63.

[0415] Aspect 65 is the coated article of Aspect 64, wherein the coating demonstrates an adhesion of 3B or higher after the acetic acid test according to ASTM D3359-22.

[0416] Aspect 66 is the coated article of Aspect 64 or 65, wherein the coating demonstrates less than 1 mm feathering after the hot feathering test.

[0417] Aspect 67 is the coated article of any one of Aspects 64 to 66, wherein the article comprises a substrate selected from aluminum, tinplate, tin-free steel, a food package, a beverage package, or a metal can.

[0418] Aspect 68 is the coated article of any one of Aspects 64 to 67, wherein the article is an easy-open-end for a beverage or food can.

[0419] Aspect 69 is a method for forming the coated article of any one of Aspects 64 to 67 comprising: coating a substrate selected from aluminum, tinplate, tin-free steel, a food package, a beverage package, or a metal can with the composition of any one of Aspects 1 in one or more layers.

[0420] Aspect 70 is the method of Aspect 69, wherein the substrate is an easy-open-end for a beverage or food can.

[0421] Aspect 71 is the method of any of Aspects 1 to 8 for forming the composition of any of Aspects 9 to 70.

[0422] Aspect 72 is the composition of any of Aspects 9 to 18, wherein the additive compound is formed according to the method of any of Aspects 1 to 8.

[0423] Aspect 73 is the composition of any of Aspects 19 to 31 , wherein the additive compound is formed according to the method of any of Aspects 1 to 8.

[0424] Aspect 74 is the composition of any of Aspects 32 to 47, wherein the additive compound is formed according to the method of any of Aspects 1 to 8.

[0425] Aspect 75 is the composition of any of Aspects 48 to 58, wherein the additive compound is formed according to the method of any of Aspects 1 to 8.

[0426] Aspect 76 is the composition of any of Aspects 59 to 70, wherein the additive compound is formed according to the method of any of Aspects 1 to 8.

[0427] Whereas particular examples of this disclosure have been described above for purposes of illustration, it will be evident to those skilled in the art that numerous variations of the details of the present disclosure may be made without departing from what is defined in the appended claims.

Claims

CLAIMSWhat is claimed is:1 . A method for synthesizing an oxazolidone compound according to Formula (I):wherein R is a connective group comprising a polyether, polyester, polyurethane, alkyl, or aromatic functional group;Ri is a terminal group comprising an epoxy, acid, hydroxyl, or amine containing group, or a non-functional group;R2 is a connective group comprising an aromatic functional group or an aliphatic functional group; and n is from 1 to 500, the method comprising:(i) reacting an isocyanate compound and an epoxy compound in the presence of a catalyst to produce an intermediate compound comprising at least two oxazolidone functional groups linked by R and comprising linking groups R2; and(ii) reacting the intermediate compound with a further compound to provide R1 end groups to produce the oxazolidone compound according to Formula (I).

2. The method of claim 1 , wherein the isocyanate compound is a diiosocyanate.

3. The method of claim 1 , wherein the isocyanate compound is an isocyanate pre-polymer prepared by reacting a polyisocyanate with a polyol in the presence of a urethane catalyst.

4. The method of claim 3, wherein the polyol is poly-tetrahydrofuran and the urethane catalyst is dibutylin dilaurate.

5. The method of any one of claims 1 to 4, wherein the epoxy compound is an aliphatic epoxy compound.

6. The method of any one of claims 1 to 4, wherein the epoxy compound is an aromatic epoxy compound.

7. The method of any one of claims 1 to 6, wherein step (i) is conducted at a temperature of from 100°C to 180°C.

8. The method of any one of claims 1 to 7, wherein the catalyst is present in an amount of from 20 ppm to 5000 ppm, based on the total weight of the isocyanate compound and the epoxy compound.

9. The method of any one of claims 1 to 8, wherein the intermediate compound comprising at least two oxazolidone functional groups linked by R and comprising linking groups R2 is acid functionalized before step (ii).

10. A powder coating composition comprising: a film forming resin; and an additive compound comprising at least two oxazolidone functionalities separated by a linking group, wherein the linking group is an aromatic functional group.11 . The composition of claim 10, wherein the additive compound further comprises: at least two connective groups, comprising, and independently selected from, at least one of an aromatic group and an aliphatic group; and optionally one or two terminal groups comprising an epoxy group.

12. The composition of claim 10 or 11 , wherein the film forming resin is a polyester-acid resin.

13. The composition of any one of claims 10 to 12, wherein the film forming resin is selected from a polyester-hydroxyl resin, an epoxy resin, and an acrylic resin.

14. The composition of any one of claims 10 to 13, wherein the additive compound further comprises a poly-THF backbone.

15. The composition of any one of claims 10 to 14, further comprising a beta- hydroxyalkyl-amide crosslinking agent.

16. The composition of any one of claims 10 to 15, further comprising a triglycidyl isocyanurate cross-linking agent.

17. The composition of any one of claims 10 to 16, further comprising a blocked isocyanate cross-linker.

18. The composition of any one of claims 10 to 17, further comprising a phenolic- based crosslinking agent.

19. The composition of any one of claims 10 to 18, wherein the connective groups are derived from bisphenol A.

20. The composition of any one of claims 10 to 19, wherein the additive compound is present in an amount from 1 wt.% to 30 wt.% based on a total weight of the composition.

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