Oxazolidinone functional compounds and coating compositions comprising oxazolidinone functional compounds

Abstract

Oxazolidinone compounds that can be used as additives in coating compositions, coating compositions comprising such additives and their use in electrocoating, powder, packaging and liquid coating applications, as well as articles coated therewith, are disclosed.

Description

[0001] Cross-reference to related applications

[0002] This application claims the benefit of U.S. Provisional Application No. 63 / 504,319, filed May 25, 2023, entitled “OXAZOLIDONE FUNCTIONAL COMPOUNDS AND COATING COMPOSITIONS INCLUDING OXAZOLIDONE FUNCTIONAL COMPOUNDS”, filed under 35 USC § 119(e), the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure relates to oxazolidinone functional compounds, coating compositions comprising oxazolidinone functional compounds, and methods for preparing and applying such coating compositions. Background Technology

[0004] The coating compositions are used to impart various functions to substrates, such as packaging for food and beverage products, and protective, decorative, and / or functional coatings for electronic, building, automotive, medical / pharmaceutical, and cosmetic products.

[0005] Coating compositions typically contain one or more film-forming components or binders, such as natural or synthetic polymers (e.g., latex or polyethylene), waxes, and self-curing and / or reaction-with-a-curing resins. Coating compositions may also contain one or more additives, solvents, pigments, or fillers that improve coating characteristics. Summary of the Invention

[0006] In one form of this disclosure, a method for synthesizing an oxazolidinone compound according to formula (I) is provided:

[0007]

[0008] Wherein R is a linking group containing a polyether, polyester, polyurethane, alkyl, or aromatic functional group; R1 is a terminal group containing a group containing an epoxy, acid, hydroxyl, or amine group, or a non-functional group; R2 is a linking group containing an aromatic or aliphatic functional group; and n is 1 to 500; the method comprises: (i) reacting an isocyanate compound with an epoxy compound in the presence of a catalyst to produce a first product containing at least two oxazolidinone functional groups linked by R and containing a linking group R2; and (ii) reacting the first product with a further compound to provide an R1 terminal group and produce a second product.

[0009] In another form, this disclosure provides compositions comprising an oxazolidinone functional compound according to formula (I):

[0010]

[0011] Where R is a linking group containing polyether, polyester, polyurethane, alkyl or aromatic functional groups; R1 is a terminal group containing an epoxy, acid, hydroxyl or amine group, or a non-functional group; R2 is a linking group containing an aromatic or aliphatic functional group; and n is 1 to 500.

[0012] In another form of this disclosure, an electrocoating composition is provided comprising: a cationic film-forming resin; and an additive compound comprising at least two oxazolidinone functional groups, wherein the additive compound has two terminal groups each comprising an amine group, and the additive compound is free of epoxy groups.

[0013] In another form of this disclosure, a powder coating composition is provided comprising: a film-forming resin; and an additive compound comprising at least two oxazolidinone functional groups separated by a linking group, wherein the linking group is an aromatic functional group.

[0014] In another form of this disclosure, a liquid coating composition is provided comprising: a polyester resin; and an additive compound comprising two oxazolidinone functional groups and at least two terminal groups, the terminal groups comprising and independently selected from at least one of epoxy groups, acid groups, hydroxyl groups, amine groups, aromatic groups and aliphatic groups.

[0015] In another form of this disclosure, a packaging coating composition is provided 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 oxazolidinone functional groups; at least two linking groups comprising aliphatic groups; and two terminal groups comprising epoxy groups. Detailed Implementation

[0016] introduce

[0017] Oxazolidinones are a class of organic compounds used in a variety of applications, such as building blocks in pharmaceuticals and monomers in the production of polymer compositions. The structure of one of the simplest oxazolidinones, 2-oxazolidinone, is shown below.

[0018]

[0019] This disclosure provides a series of coating compositions comprising oxazolidinone functional compounds, i.e., compounds containing one or more oxazolidinone functional groups, as resins or additives in coating formulations. These oxazolidinone functional compounds can be oligomers or polymers. Oxazolidinone compounds can 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.

[0020] One of the advantages of using oxazolidinones in coating compositions is their versatility. Depending on the specific application requirements, they can be used in combination with a wide variety of coatings, curing agents, and resins. Furthermore, oxazolidinone functional compounds typically have low VOCs, making them an attractive option for environmentally friendly coating compositions.

[0021] definition

[0022] For the purposes of the following detailed description, it should be understood that this disclosure may take various alternative variations and sequences of steps, unless the contrary is explicitly stated. Furthermore, except in any operational instance or where otherwise indicated, all figures representing quantities of ingredients used, for example, in the specification and claims, should in all cases be understood to be modified by the term “about.” Therefore, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary according to the desired properties to be obtained through this disclosure. At least, and without attempting to limit the application of the equivalence principle to the scope of the claims, each numerical parameter should be interpreted at least according to the number of significant figures reported and by applying ordinary rounding techniques.

[0023] Although the numerical ranges and parameters described in this disclosure are approximate, the values ​​illustrated in specific examples are reported as precisely as possible. However, any numerical value inherently contains some error that is necessarily caused by the standard deviation found in its corresponding test measurement results.

[0024] Furthermore, it should be understood that any numerical range described herein is intended to include all subranges thereof. For example, the range “1 to 10” is intended to include all subranges between the stated minimum value of 1 and the stated maximum value of 10, that is, a minimum value equal to or greater than 1 and a maximum value equal to or less than 10.

[0025] In this application, unless otherwise specified, the use of the singular includes the plural, and the plural encompasses the singular. Additionally, in this application, unless otherwise specified, the use of "or" means "and / or," even if "and / or" may be explicitly used in certain circumstances. Furthermore, in this application, unless otherwise specified, the use of "an / a" means "at least one / a." For example, "an" polymer, "an" pigment, "an" composition, "an" powder coating composition, "an" effect pigment, "an" polymer resin particle, etc., all refer to one or more of these terms.

[0026] "Polymer" refers to oligomers, homopolymers (e.g., prepared from a single monomer species), copolymers (e.g., prepared from at least two monomer species), terpolymers (e.g., prepared from at least three monomer species), and graft polymers.

[0027] "Film-forming resin" refers to a resin that can form a self-supporting continuous film on at least the horizontal surface of a substrate upon removal of any diluent or carrier.

[0028] A "crosslinking agent" is a molecule that contains two or more functional groups that are reactive with other functional groups and can connect two or more monomers or polymers through chemical bonds.

[0029] "Cat-electrodepositable adhesives" or "cationic film-forming resins" refer to organic resin polymers containing cationic groups (which can be at least partially neutralized to form cationic salt groups), which impart a positive charge to the polymer and enable the polymer to be deposited onto a conductive substrate by a cationic electrodeposition process.

[0030] "Colorant" refers to a pigment, colorant, dye, or any other coloring material used to impart color or opacity to a powder coating composition, according to ASTM E284. As used herein, the term "colorant" is distinct from effect pigments.

[0031] As used herein, “substantially free” means that the composition contains 0.5 wt.% or less of the material under discussion based on the total weight of the composition.

[0032] The “low VOC” indicator composition used herein has a volatile organic compound (VOC) content of less than 45 g / L as calculated according to EPA Method 24.

[0033] I. Synthesis

[0034] The oxazolidinone compounds disclosed herein can be synthesized via a multi-stage procedure comprising a first stage of synthesizing oxazolidinone functional adducts and an optional second stage of adding functional groups to the first stage.

[0035] The oxazolidinone compounds produced by the synthesis described herein can have the following formula (I):

[0036]

[0037] Each R is independently a linking group containing a polyether, polyester, polyurethane, alkyl, or aromatic functional group; each R1 is independently a terminal group containing an epoxy, acid, hydroxyl, urethane, or amine group, or a non-functional group; each R2 is independently a linking group containing an aromatic or aliphatic functional group; and n is 1 to 500. Each R, R1, and R2 may be the same or different in formula (I).

[0038] The first stage of synthesis may include reacting an isocyanate compound with an epoxide compound in the presence of a catalyst to produce a first product. This first product may contain at least two oxazolidinone functional groups linked by R and include a linking group R2.

[0039] The second stage of synthesis may include reacting the first product with another compound to provide an R1 terminal group to produce a second product. The other compounds in the second group, part, etc., may be any functional group.

[0040] In the first stage, oxazolidinone compounds can be synthesized by reacting aliphatic epoxy compounds, aromatic epoxy compounds, and diisocyanate or isocyanate prepolymers in the presence of a catalyst.

[0041] Aliphatic epoxy compounds include any compound containing both aliphatic and epoxy functional groups. Aromatic epoxy compounds include any compound containing both aromatic and epoxy functional groups.

[0042] Suitable aliphatic and aromatic epoxy compounds include reaction products of glycidyl ethers (such as epichlorohydrin) and bisphenol compounds (such as bisphenol A). Also suitable are C4-C28 alkyl glycidyl ethers; C2–C28 alkyl and alkenyl glycidyl esters; C1–C28 alkyl, monophenol and polyphenol glycidyl ethers; catechol, resorcinol, hydroquinone, 4,4'-dihydroxydiphenylmethane (or bisphenol F), 4,4'-dihydroxy-3,3'-dimethyldiphenylmethane, 4,4'-dihydroxydiphenyldimethylmethane (or bisphenol A), 4,4'-dihydroxydiphenylmethylmethane, 4,4'-dihydroxydiphenylcyclohexane, 4,4'-dihydroxy-3,3'-dimethyldiphenylpropane, 4,4'-dihydroxydiphenylsulfone and tris(4-hydroxyphenyl)methane polyglycidyl ethers; polyglycidyl ethers of the chlorination and bromination products of the above-mentioned bisphenols; and polyglycidyl ethers of phenolic varnishes. ; polyglycidyl ethers of diphenols obtained by esterifying the ethers of diphenols obtained by esterifying the salts of aromatic hydroxycarboxylic acids with dihaloalkanes or dihalodialkyl ethers; polyglycidyl ethers of polyphenols obtained by condensing phenol with long-chain halogenated alkanes containing at least two halogen atoms; N,N'-diglycidyl-aniline; N,N'-dimethyl-N,N'-diglycidyl-4,4'-diaminodiphenylmethane; N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane; N,N'-diglycidyl-4-aminophenylglycidyl ether; N,N,N',N'-tetraglycidyl-1,3-propylene bis-4-aminobenzoate; phenolic epoxy resins; cresolic epoxy resins; 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.

[0043] Diisocyanates are isocyanate compounds 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), dodecanethylene diisocyanate, 1,4-diisocyanate cyclohexane, 3-isocyanate methyl-3,3,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), diisocyanate dicyclohexylmethane (H12-MDI), and diphenylmethane diisocyanate (M... DI), 4,4'-diisocyanate-3,3'-dimethyldicyclohexylmethane, 4,4'-diisocyanate-2,2-dicyclohexylpropane, poly(hexamethylene diisocyanate), octamethylene diisocyanate, toluene-α,4-diisocyanate, methyl phenyl-2,4-diisocyanate-terminated poly(propylene glycol), methyl phenyl-2,4-diisocyanate-terminated polyethylene adipate, 2,4,6-trimethyl-1,3-phenylene diisocyanate, 4-chloro-6-methyl-1,3-phenylene diisocyanate Isocyanates, poly[1,4-phenylene diisocyanate-co-poly(1,4-butanediol)] diisocyanate, poly(tetrafluoroethylene oxide-co-difluoromethylene oxide) α,ω-diisocyanate, 1,4-diisocyanate butane, 1,8-diisocyanate octane, 1,3-bis(1-isocyanate-1-methylethyl)benzene, 3,3'-dimethyl-4,4'-biphenyl diisocyanate, naphthalene-1,5-diisocyanate, 1,3-phenylene diisocyanate, 1,4-diisocyanate benzene, 2,4- or 2, 5- or 2,6-diisocyanate toluene (TDI) or a mixture of these isomers, 4,4'-, 2,4- or 2,2'-diisocyanate diphenylmethane or a mixture of these isomers, 4,4-, 2,4'- or 2,2'-diisocyanate-2,2-diphenylpropane-p-xylene diisocyanate and α,α,α',α'-tetramethyl-m- or-p-xylene diisocyanate (TMXDI), a mixture thereof or biuret, isocyanurate, carbamate or diuret of the above isocyanates.

[0044] Isocyanate-terminated prepolymers can also be used as a source of NCO groups in the reaction. These prepolymers can be prepared by reacting excess polyisocyanate with polyols or alcohols in the presence of a polyurethane catalyst. Carbamate catalysts can catalyze the formation of carbamate bonds.

[0045] Polyisocyanates and diisocyanates suitable for preparing isocyanate prepolymers include, but are not limited to, alkylene isocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (“HDI”), 1,2-propylene diisocyanate, 1,2-butene diisocyanate, 2,3-butene diisocyanate, 1,3-butene diisocyanate, ethylene diisocyanate, and butylene diisocyanate, as well as cycloalkylene isocyanates such as 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,2-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl) isocyanate (“HMDI”), and cyclotrimers of 1,6-hexamethylene diisocyanate (also known as isocyanurate trimers of HDI, which can be obtained from Convestro Desmodur N3300). (Available commercially from AG) and m-tetramethylxylene diisocyanate (available commercially from Allnex SA for TMXDI®). Aromatic polyisocyanates may also be used, including (i) aryl isocyanates such as m-phenylene diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate and 1,4-naphthalene diisocyanate; and (ii) arylalkyl isocyanates such as 4,4'-diphenylmethane (“MDI”), 2,4-methylphenylene diisocyanate or 2,6-methylphenylene diisocyanate (“TDI”) or mixtures thereof, 4,4-toluidine diisocyanate and xylene diisocyanate. Triisocyanates, such as triphenylmethane-4,4',4''-triisocyanate, 1,3,5-triisocyanatobenzene, and 2,4,6-triisocyanatotoluene, can also be used; tetraisocyanates, such as 4,4'-diphenyldimethylmethane-2,2',5,5'-tetraisocyanate; and polymeric polyisocyanates, such as methylphenylene diisocyanate dimers and trimers. Suitable polyisocyanates also include blocked polyisocyanates selected from polymeric polyisocyanates (such as polymeric HDI, polymeric MDI, polymeric isophorone diisocyanate, etc.). Polyisocyanates can also be blocked trimers of hexamethylene diisocyanate, which can be obtained from Covestro AG using Desmodur N3300®. Mixtures of the above-mentioned polyisocyanates can also be used.

[0046] Polyols used to prepare isocyanate prepolymers may include, but are not limited to, any material containing reactive hydrogen atoms and capable of reacting with isocyanate or isocyanurate groups. These materials include hydroxyl-functional acrylics, hydroxyl-functional polyesters, hydroxyl-functional polyethers, polyamines, polyamides, short-oil alkyd resins, castor oil, epoxy resins with secondary hydroxyl groups, phenolic resins, and hydroxyl-functional vinyl resins. Suitable polyols include, but are not limited to, ethylene glycol, propylene glycol, butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, glycerol, trimethylolpropane, and pentaerythritol. Suitable polyols also include poly(tetrahydrofuran).

[0047] Alcohols suitable for preparing isocyanate prepolymers include, but are not limited to, aliphatic, alicyclic, or aromatic alkyl monohydric alcohols or phenolic compounds, including, for example, lower aliphatic alcohols such as methanol, ethanol, and n-butanol; alicyclic alcohols such as cyclohexanol; aromatic alkyl alcohols such as phenylmethanol and methylphenylmethanol; and phenolic compounds such as phenol itself and substituted phenols, wherein the substituents do not affect the coating operation, such as cresol and nitrophenol.

[0048] The polyurethane catalyst suitable for preparing isocyanate prepolymers can be any known polyurethane catalyst, such as organotin compounds or amine catalysts. Suitable catalysts include dibutyltin dilaurate, dibutyltin diacetate, diethyltin diacetate, dihexyltin diacetate, di-2-ethylhexyltin oxide, dioctyltin dioxide, stannous octoate, stannous oleate, or mixtures thereof.

[0049] The synthesis of isocyanate prepolymers can involve reacting an excess of polyisocyanate with a polyol or alcohol at temperatures 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 covered by any two of the aforementioned values ​​as endpoints. For example, the reaction can be carried out at temperatures of 60°C to 90°C, 65°C to 85°C, or 70°C to 80°C. During the reaction, the polyol or alcohol can be slowly added to the reaction mixture, for example, over a period of 1 hour or 2 hours.

[0050] Suitable catalysts for the first stage of oxazolidinone 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 lithium butoxy; 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; phosphine, such as triphenylphosphine; phosphonium compounds, such as allyltriphenylphosphonium bromide, diallyldiphenylphosphonium bromide, ethyltriphenylphosphonium chloride, ethyltriphenylphosphonium iodide, tetrabutylacetic acid phosphonium-acetic acid complex, tetrabutylacetic acid phosphonium, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, and tetrabutylphosphonium iodide; combinations of triphenylantimony and iodine; and imidazoles, such as 2-phenylimidazolium and 2-methylimidazolium. The catalysts listed above may be used alone or in combination of two or more of them. Based on the total weight of the reagents in the first stage of synthesis, the catalyst may be present in amounts 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 covered by any two of the foregoing values ​​as endpoints. For example, the catalyst may be present in amounts of 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 500 ppm to 1000 ppm.

[0051] The first stage of oxazolidinone compound synthesis may involve loading an aliphatic or aromatic epoxy compound, a diisocyanate or isocyanate prepolymer, and a catalyst into a reaction vessel.

[0052] The reaction can be carried out in a reactor with sufficient stirring to produce a homogeneous reaction mixture. Suitable stirring can be achieved using a mechanical stirrer. The reactor vessel can be connected to a heating medium to maintain a suitable reaction temperature. The reactor vessel can also be connected to a cooling bath with any suitable cooling medium to maintain a suitable reaction temperature. The reactor vessel can also be sealed to create a high-pressure environment for carrying out the reaction.

[0053] The reaction can be carried out at temperatures 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 covered by any two of the aforementioned values ​​as endpoints. For example, the reaction can be carried out at temperatures between 100°C and 180°C, 120°C and 180°C, 130°C and 170°C, or 140°C and 160°C.

[0054] The second stage of oxazolidinone synthesis can be used to add functional groups, such as acid, hydroxyl, or amine groups, to the oxazolidinone compound from the first stage. The reaction involves adding a carboxylic acid-functionalized compound or an amine compound to the first-stage adduct to form a hydroxyl or amine-functionalized oxazolidinone. Suitable carboxylic acid-functionalized compounds include adipic acid. The formed hydroxyl-functionalized oxazolidinone can be further converted to an acid-functionalized oxazolidinone by reacting the hydroxyl group with an acid anhydride compound. Suitable acid anhydrides include cyclic dicarboxylic acid anhydrides, such as methylhexahydrophthalic anhydride (MHHPA).

[0055] Prior to the second stage of synthesis, the oxazolidinone compounds from the first stage can be acid-functionalized using carboxylic acid functional compounds such as adipic acid.

[0056] The second stage of synthesis may include further converting the epoxide into an oxazolidinone by heating the mixture of the first-stage adduct and the monoisocyanate compound under the same reaction conditions as the first stage.

[0057] II. Compositions containing oxazolidinone functional compounds

[0058] This disclosure provides a resin composition comprising an oxazolidinone compound and / or a compound according to formula (I):

[0059] Formula (I)

[0060]

[0061] In formula (I), each R can independently be a polyether, polyester, polyurethane, alkyl, or aromatic group; each value of R1 can independently be a group containing an epoxy, acid, hydroxyl, urethane, or amine, or a non-functional group; each R2 can independently contain an aromatic or aliphatic functional group; and n can be any integer from 1 to 500, including 1, 500, and all integers therein, and any range including any two of such integers as endpoints. The values ​​of R, R1, and R2 can be the same or different.

[0062] Suitable aromatic moieties include divalent moieties with 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).

[0063] Suitable alkyl or aliphatic groups include any straight-chain or branched C2 to C3 groups. 30 Groups, including C2, C 30 and all integers in between, and any range including any two of such integers as endpoints.

[0064] The resin composition may also be substantially free of epoxy groups.

[0065] The resin composition may also be substantially free of crosslinking agents, such as phenolic crosslinking agents, amine-based crosslinking agents, isocyanates, sulfur-containing compounds (such as thiols and thiols).

[0066] The resin composition 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 in any range covered by any two of the foregoing values ​​as endpoints. For example, the resin composition may have a weight / number average molecular weight of 400 g / mol to 10,000 g / mol, 500 g / mol to 8,000 g / mol, 1,000 g / mol to 7,000 g / mol, 2,000 g / mol to 6,000 g / mol, or 3,000 g / mol to 5,000 g / mol as determined below.

[0067] As discussed below, the oxazolidinone compounds of the present invention can be formulated into a variety of coating compositions for various end-use applications, such as E-coatings, powder coatings, liquid and roll coating compositions, and packaging coatings.

[0068] The following are examples of oxazolidinone functional compounds.

[0069]

[0070] IV.E-Coating Composition

[0071] As a coating application method, electrodeposition involves depositing a film-forming composition onto a conductive substrate under the influence of an applied electric potential. Electrodeposition has become the standard in the coating industry because, compared to non-electrophoretic coating methods, it offers increased paint utilization, less waste, improved substrate corrosion protection, and minimal environmental pollution.

[0072] This disclosure provides an electrodeposable coating (e-coating or E-coating) composition comprising a cationic electrodeposable binder.

[0073] This disclosure provides an electrocoating composition comprising a cationic film-forming resin and an additive comprising an oxazolidinone functional group. The electrocoating composition may also include an optional curing agent.

[0074] As described above, the cationic electrodepositable adhesive comprises a film-forming polymer containing cationic salt groups. Film-forming polymers containing cationic salt groups can be used in cationic electrodepositable coating compositions. As used herein, the term "film-forming polymer containing cationic salt groups" refers to a polymer containing at least partially neutralized cationic groups such as positively charged sulfonium, ammonium, or phosphonium groups.

[0075] Film-forming polymers containing cationic salt groups include functional groups. The functional groups of film-forming polymers containing cationic salt groups may include active hydrogen functional groups. The term "active hydrogen" refers to hydrogen that, according to the Zelevityan test, exhibits activity due to the position of said hydrogen in the molecule, as described in the JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, Vol. 49, p. 3181 (1927). Therefore, active hydrogen contains hydrogen atoms bonded to oxygen, nitrogen, or sulfur, and thus useful compounds will contain those having at least two hydroxyl, thiol, primary amine, and / or secondary amine groups (in any combination). Film-forming polymers containing cationic salt groups and active hydrogen functional groups can be referred to as film-forming polymers containing active hydrogen and cationic salt groups.

[0076] Polymers suitable for use as film-forming polymers containing cationic salt groups in this invention include, but are not limited to, alkyd resin polymers, acrylic acid, polyepoxides, polyamides, polyurethanes, polyureas, polyethers, and polyesters.

[0077] More specifically, suitable film-forming polymers containing active hydrogen and cationic salt groups include polyepoxide-amine adducts, such as adducts of polyglycidyl ethers of polyphenols (e.g., bisphenol A) with primary and / or secondary amines. A portion of the amine reacting with the polyepoxide can be a ketimine of the polyamine. Ungelled polyepoxide-polyoxyethylene polyamine resins are also suitable. Alternatively, cationic acrylic resins can be used.

[0078] In addition to resins containing amine salt groups, resins containing quaternary ammonium salt groups can also be used as film-forming polymers containing cationic salt groups in this invention. These resins include those formed by reacting organic polyepoxides with tertiary ammonium salts.

[0079] Other suitable cationic resins include resins containing ternary sulfonate groups. Alternatively, cationic resins cured via transesterification can also be used.

[0080] Other suitable film-forming polymers containing cationic salt groups include those capable of forming photodegradable electrodepositable coating compositions. Such polymers include those containing cationic amine salt groups derived from side chains and / or amino groups. Also suitable are resins containing active hydrogen and cationic salt groups derived from polyglycidyl ethers of polyphenols bonded to more than one aromatic group. Also suitable are polypropylene oxide resins, such as DER-732, commercially available from Palmer Holland.

[0081] By at least partially neutralizing with a neutralizing acid, a film-forming polymer containing active hydrogen and cationic salt groups becomes cationic and water-dispersible. 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 aminosulfonic acids. "Aminosulfonic acid" means aminosulfonic acid itself or its derivatives, such as aminosulfonic acids or their derivatives having the following formula:

[0082]

[0083] Wherein R is hydrogen or an alkyl group having 1 to 4 carbon atoms. Mixtures of the acids mentioned above can also be used in this invention.

[0084] The degree of neutralization of film-forming polymers containing cationic salt groups can vary depending on the specific polymer involved. However, sufficient neutralizing acid should be used to adequately neutralize the film-forming polymers containing cationic salt groups so that they can be dispersed in an aqueous dispersion medium. For example, the amount of neutralizing acid used may provide at least 20% of the total theoretical neutralization. An excess of neutralizing acid, exceeding 100% of the total theoretical neutralization, may also be used. For example, based on the total amines in the film-forming polymer containing active hydrogen and cationic salt groups, the amount of neutralizing acid used to neutralize the film-forming polymer containing active hydrogen and cationic salt groups may be ≤100%. The total amount of neutralizing acid used to neutralize the film-forming polymer containing cationic salt groups can range from any combination of the values ​​stated in the preceding sentences (including the stated values). For example, based on the total amines in the film-forming polymer containing cationic salt groups, the total amount of neutralizing acid used to neutralize the film-forming polymer containing active hydrogen and cationic salt groups may be 20%, 35%, 50%, 60%, or 80%.

[0085] According to this disclosure, based on the total weight of the electrocoating composition, the film-forming polymer containing cationic salt groups may be present in the cationic electrodepositable coating composition in amounts 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 covered by any two of the foregoing values. For example, the film-forming polymer containing cationic salt groups may be present in amounts 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.%.

[0086] According to this disclosure, the cationic electrodepositable adhesive of the cationic electrodepositable coating composition of the present invention may optionally further include a curing agent. The curing agent reacts with functional groups on the film-forming polymer. For example, the curing agent may react with reactive groups (such as active hydrogen groups) of the film-forming polymer containing cationic salt groups to achieve curing of the coating composition to form a coating. As used herein, the terms “cured,” “cured,” or similar terms used in conjunction with the cationic electrodepositable coating composition described herein mean that at least a portion of the components forming the cationic electrodepositable coating composition crosslinks to form a coating. Furthermore, curing of the cationic electrodepositable coating composition refers to subjecting the composition to curing conditions (e.g., elevated temperatures) that cause the reactive functional groups of the components of the cationic electrodepositable coating composition to react, and cause the components of the composition to crosslink and form a coating that is at least partially cured. Suitable curing agents are at least partially blocked polyisocyanates, amino plastic resins, and phenolic plastic resins, such as phenol-formaldehyde condensates, including their allyl ether derivatives.

[0087] Suitable at least partially blocked polyisocyanates include aliphatic polyisocyanates, aromatic polyisocyanates, and mixtures thereof. Curing agents may include at least partially blocked aliphatic polyisocyanates. Suitable at least partially blocked aliphatic polyisocyanates include, for example, fully blocked aliphatic polyisocyanates, or partially blocked aliphatic polyisocyanates that react with the polymer backbone. "Blocked" means that the isocyanate groups have reacted with the compound such that the resulting blocked isocyanate groups are stable to active hydrogen at ambient temperatures but react with active hydrogen in the film-forming polymer at elevated temperatures (such as between 90°C and 200°C). Polyisocyanate curing agents may be fully blocked polyisocyanates that have substantially no free isocyanate groups.

[0088] Polyisocyanate curing agents may include diisocyanates, higher-functionality polyisocyanates, or combinations thereof. For example, polyisocyanate curing agents may include aliphatic polyisocyanates and / or aromatic polyisocyanates. Aliphatic polyisocyanates may comprise (i) alkylene isocyanates, such as trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (“HDI”), 1,2-propylene diisocyanate, 1,2-butene diisocyanate, 2,3-butene diisocyanate, 1,3-butene diisocyanate, ethylene diisocyanate, and butylene diisocyanate, and (ii) cycloalkylene isocyanates, such as 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,2-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl) isocyanate (“HMDI”), cyclotrimers of 1,6-hexamethylene diisocyanate (also known as isocyanurate trimers of HDI, which can be obtained from Convestro Desmodur N3300). (Available commercially from AG) and m-tetramethylxylene diisocyanate (available commercially from Allnex SA at TMXDI®). Aromatic polyisocyanates may comprise (i) aryl isocyanates, such as m-phenylene diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate and 1,4-naphthalene diisocyanate, and (ii) arylalkyl isocyanates, such as 4,4'-diphenylmethane (“MDI”), 2,4-methylphenylene diisocyanate or 2,6-methylphenylene diisocyanate (“TDI”) or mixtures thereof, 4,4-toluidine diisocyanate and xylene diisocyanate. Triisocyanates, such as triphenylmethane-4,4',4''-triisocyanate, 1,3,5-triisocyanatobenzene, and 2,4,6-triisocyanatotoluene, can also be used; tetraisocyanates, such as 4,4'-diphenyldimethylmethane-2,2',5,5'-tetraisocyanate; and polymeric polyisocyanates, such as methyl phenylene diisocyanate dimers and trimers. The curing agent may contain a terminal polyisocyanate selected from polymeric polyisocyanates (such as polymeric HDI, polymeric MDI, polymeric isophorone diisocyanate, etc.). The curing agent may also contain a hexamethylene diisocyanate-terminated trimer, which is commercially available from Covestro AG using Desmodur N3300®. Mixtures of polyisocyanate curing agents can also be used.

[0089] Polyisocyanate curing agents can be at least partially end-capped with at least one end-capping agent selected from the following: 1,2-alkyldiol, for example, 1,2-propanediol; 1,3-alkyldiol, for example, 1,3-butanediol; benzyl alcohol, for example, benzyl alcohol; allyl alcohol, for example, allyl alcohol; caprolactam; dialkylamine, for example, dibutylamine; and mixtures thereof. Polyisocyanate curing agents can also be at least partially end-capped with at least one 1,2-alkyldiol having three or more carbon atoms (e.g., 1,2-butanediol).

[0090] Other suitable end-capping agents include aliphatic, alicyclic, or aromatic alkyl monohydric alcohols or phenolic compounds, including, for example, lower aliphatic alcohols such as methanol, ethanol, and n-butanol; alicyclic alcohols such as cyclohexanol; aromatic alkyl alcohols such as phenylmethanol and methylphenylmethanol; and phenolic compounds such as phenol itself and substituted phenols, wherein the substituents do not affect the coating operation, such as cresol and nitrophenol. Ethylene glycol ethers and ethylene glycol amines can also be used as end-capping agents. Suitable ethylene glycol ethers include ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether, and propylene glycol methyl ether. Other suitable end-capping agents include oximes such as methyl ethyl ketone oxime, acetone oxime, and cyclohexanone oxime.

[0091] For example, the blocking agent may include an ether or polyether containing a hydroxyl group and a terminal group having the structure -OR, wherein R is a C1 to C4 alkyl group, such as a C1 to C3 alkyl group. Such blocking groups may include the following structures:

[0092]

[0093] Where R1 is hydrogen or methyl, R2 is a C1 to C4 alkyl group, such as a C1 to C3 alkyl group; and n is an integer from 1 to 6.

[0094] The curing agent may optionally contain high molecular weight volatile groups. As used herein, the term "high molecular weight volatile groups" refers to blocking agents and other organic byproducts that are generated and volatilized during the curing reaction of the electrodeposable 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 be in the range of 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, organic byproducts may include alcohol byproducts generated from the reaction of the film-forming polymer and the curing agent of amino or phenolic plastics, and the blocking agent may contain organic compounds, including alcohols, for blocking the isocyanate groups of the polyisocyanate that are not blocked during curing. For clarity, high molecular weight volatile groups are covalently bonded to the curing agent prior to curing, and any organic solvents that may be present in the electrodeposable coating composition are explicitly excluded. During curing, the pigment to binder ratio of the deposited film in the cured film may increase relative to the uncured pigment to binder ratio deposited in the electrodeposable coating composition, due to the loss of higher quality blocking agents and other organic byproducts derived from the curing agent volatilizing during curing. Based on the total weight of the film-forming binder, high molecular weight volatile groups may account for 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% by weight, such as 13% to 30% by weight. Based on the total weight of the film-forming adhesive before and after curing, the high molecular weight volatile groups and other low molecular weight volatile organic compounds generated during curing, such as low molecular weight sealants and organic byproducts generated during curing, may be present in amounts such that the relative weight loss of the film-forming adhesive deposited on the substrate relative to the weight of the cured film-forming adhesive is 5% to 50% by weight, such as 7% to 45% by weight, such as 9% to 40% by weight, such as 11% to 35% by weight, such as 13% to 30% by weight.

[0095] Curing agents may include amino plastic resins. Amino plastic resins are condensation products of aldehydes and substances carrying amino or amide groups. Condensation products obtained from the reaction of alcohols and aldehydes with melamine, urea, or benzomelamine can be used. However, condensation products of other amines and amides can also be used, such as aldehyde condensates of alkyl and aryl-substituted derivatives of triazine, diazine, triazole, guanidine, guanidineamine, and alkyl and aryl-substituted ureas and alkyl and aryl-substituted melamines. Suitable compounds are N,N'-dimethylurea, phenylurea, dicyandiamide, formylguanidine, acetylguanidine, cyanuric acid diamide, 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, etc. Suitable aldehydes include formaldehyde, acetaldehyde, crotonaldehyde, acrolein, benzaldehyde, furfural, glyoxal, etc.

[0096] Amino plastic resins may contain hydroxymethyl groups or similar alkyl alcohol groups, and at least a portion of these alkyl alcohol groups may be etherified by reaction with an alcohol to provide a resin soluble in organic solvents. For this purpose, any monohydric alcohol may be used, including alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, and other alcohols, as well as benzyl alcohol and other aromatic alcohols, cyclic alcohols such as cyclohexanol, monoethers of ethylene glycol such as cellosolve and carbitol, and halogenated or other substituted alcohols such as 3-chloropropanol and butoxyethanol.

[0097] Suitable commercially available amino plastic resins are those from Allnex Belgium SA / NV under the trademark CYMEL® (such as CYMEL 1130 and 1156) and from INEOS Melamines under the trademark RESIMENE® (such as RESIMENE 750 and 753). Suitable amino plastic resins also include those described in column 16, line 3 through column 17, line 47 of U.S. Patent No. 3,937,679, this portion of which is hereby incorporated by reference. As disclosed in the foregoing portion of the '679 patent, amino plastics can be used in combination with methanol phenol ethers.

[0098] Phenolic resins are formed by the condensation of aldehydes and phenols. Suitable aldehydes include formaldehyde and acetaldehyde. Methylene releasers and aldehyde releasers (such as paraformaldehyde and hexamethylenetetramine) can also be used as aldehyde agents. Various phenols can be used, such as phenol itself, cresol, or substituted phenols, wherein a hydrocarbon group having a straight-chain, branched, or cyclic structure replaces hydrogen in an aromatic ring. Mixtures of phenols can also be used. Some specific suitable phenols are p-phenylphenol, p-tert-butylphenol, p-tert-amylphenol, cyclopentylphenol, and unsaturated hydrocarbon-substituted phenols, such as monobutenylphenol containing a butenyl group at the ortho, meta, or para position, wherein the double bond appears at various positions in the hydrocarbon chain.

[0099] As described above, amino plastic resins and phenolic plastic resins are described in column 6, line 20 through column 7, line 12 of U.S. Patent No. 4,812,215, the referenced portion of which is incorporated herein by reference.

[0100] Based on the total weight of the electrocoating composition, the curing agent may be present in the cationic electrodepositable coating composition in amounts 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 any range covered by any two of the foregoing values. For example, the curing agent may be present in amounts 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.%.

[0101] The e-coating composition may also contain additives containing oxazolidinone groups. For example, the additive may contain at least two oxazolidinone functional groups. The chemical structure of the additive may also be a linking group chemically bonded to the oxazolidinone functional groups and terminal groups. The linking group may be an aromatic functional group and / or an aliphatic functional group. Terminal groups may be at each end of the oxazolidinone functional additive and bonded to the linking group. The terminal groups may contain amine groups. The entire oxazolidinone additive structure may also be free of epoxy groups.

[0102] The structures of oxazolidinone additives are shown in Table 1 below:

[0103] Table 1

[0104] E-coated oxazolidinone structure

[0105]

[0106] Coating compositions containing oxazolidinone additives may have an oxazolidinone group equivalent per coating weight as low as 100 g / equivalent weight, 200 g / equivalent weight, 300 g / equivalent weight, 400 g / equivalent weight, 500 g / equivalent weight, 600 g / equivalent weight, 700 g / equivalent weight, 800 g / equivalent weight, 900 g / equivalent weight or as high as 1,000 g / equivalent weight, 1,100 g / equivalent weight, 1,200 g / equivalent weight, 1,300 g / equivalent weight, 1,400 g / equivalent weight, 1,500 g / equivalent weight, 1,600 g / equivalent weight, 1,700 g / equivalent weight, 1,800 g / equivalent weight, 1,900 g / equivalent weight, 2,000 g / equivalent weight or any range covered by any of the foregoing values ​​as endpoints. For example, the equivalent of oxazolidinone groups per coating weight can be from 100 g / equivalent weight to 1,500 g / equivalent weight, from 200 g / equivalent weight to 1,000 g / equivalent weight, or from 300 g / equivalent weight to 700 g / equivalent weight.

[0107] The oxazolidinone additive may be present in the E-coating composition in amounts 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 covered by any two of the foregoing values ​​as endpoints. For example, based on the total weight of the E-coating composition, the oxazolidinone additive may be present in amounts from 1 wt.% to 13 wt.%, 2 wt.% to 12 wt.%, 3 wt.% to 11 wt.%, or 4 wt.% to 10 wt.%.

[0108] The cationic electrodepositable coating compositions of the present invention can be applied to a variety of substrates. Therefore, the present invention further relates to a substrate at least partially coated with a coating deposited by the cationic electrodepositable coating compositions described herein. It should be understood that the cationic electrodepositable coating compositions can be applied to the substrate as a single coating or as a coating in a multilayer coating composite. The cationic electrodepositable coating compositions can be electrophoretically deposited on any conductive substrate. Suitable substrates include metallic substrates, metallic alloy substrates, and / or metallized substrates, such as nickel-plated plastics. Additionally, the substrate can contain non-metallic conductive materials, including composite materials, such as materials containing, for example, carbon fibers or conductive carbon. According to the present invention, the metal or metallic alloy can include cold-rolled steel, hot-rolled steel, zinc-coated steel, zinc compounds, or zinc alloys, such as electro-galvanized steel, hot-dip galvanized steel, alloyed hot-dip galvanized steel, and zinc-plated steel. Aluminum alloys of the 2XXX, 5XXX, 6XXX, or 7XXX series, as well as clad aluminum alloys and cast aluminum alloys of the A356 series, can also be used as substrates. Magnesium alloys from the AZ31B, AZ91C, AM60B, or EV31A series can also be used as the substrate. The substrate used in this invention may also include titanium and / or titanium alloys. Other suitable non-ferrous metals include copper and magnesium, as well as alloys of these materials. Suitable metallic substrates for use in this invention include those commonly used in: vehicle body assemblies (e.g., but not limited to doors, body panels, trunk lids, top panels, hoods, top and / or longitudinal beams, rivets, landing gear assemblies, and / or skins used on aircraft), vehicle frames, vehicle components, motorcycles, wheels, industrial structures and components such as household appliances including washing machines, dryers, refrigerators, stoves, dishwashers, etc., agricultural equipment, lawn and garden equipment, air conditioning units, heat pump units, lawn furniture, and other articles of manufacture. As used herein, “vehicle” or variations thereof include, but are not limited to, civil, commercial, and military aircraft and / or land vehicles, such as automobiles, motorcycles, and / or trucks. Metallic substrates may also be in the form of, for example, metal sheets or prefabricated parts. It should also be understood that the substrate can be pretreated with pretreatment solutions including zinc phosphate pretreatment solutions, such as those described, for example, in U.S. Patent Nos. 4,793,867 and 5,588,989, or zirconium-containing pretreatment solutions.

[0109] The coating composition can be applied as a single layer to an uncoated substrate. For example, the coating composition can be applied to the substrate to form a single coating. As used herein, "single coating" refers to a single coating without any additional coating. Therefore, the coating composition can be applied directly to the substrate and cured to form a single coating, i.e., a single layer.

[0110] The coated substrate of this disclosure may further comprise one or more additional coatings, such as a second outer coating deposited onto at least a portion of the first coating composition, to form a multilayer coating, as by applying a topcoat. When forming a multilayer coating, the first coating composition may be cured before applying the additional outer coatings, or one or more of the additional outer coatings and the first coating composition may be cured simultaneously. It should be understood that the second outer coating and the additional outer coatings may be in solid or liquid form. The coating composition may be layered under a topcoat or a series of topcoats to form a stack. The coating composition may be a first layer applied as a base coat or primer to a bare substrate. The primer may then have subsequent layers applied on top of it to form a multilayer coating.

[0111] The electrocoated articles envisioned in this disclosure can have low scribing creep as measured according to ASTM B117-19. For example, the coated articles can have scribing 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%.

[0112] The electrocoated articles envisioned in this disclosure can also achieve high scores in cross-cut adhesion tests, as measured according to ASTM D3359-22. The coating can exhibit grades of 0B or higher, 1B or higher, 2B or higher, 3B or higher, 4B or higher, or 5B.

[0113] IV. Powder Coating Compositions

[0114] Powder coating is a solvent-free or low-solvent coating system used in a variety of applications, including automotive coatings, home appliances, building and construction components, furniture, agricultural machinery, and electronic products. Powder coatings are made from thermosetting resin systems and are typically applied to a substrate electrostatically and cured at elevated temperatures (e.g., 300℉ or above).

[0115] This disclosure provides a powder coating composition comprising a film-forming resin and an additive containing an oxazolidinone functional group. The powder coating composition may also include an optional curing agent.

[0116] The powder coating compositions according to this disclosure may comprise any of a variety of thermosetting powder coating compositions known in the art. As used herein, the term "thermosetting" refers to a composition that irreversibly "solidifies" upon curing or crosslinking, wherein the polymer chains of the polymer components are linked together by covalent bonds. This characteristic is generally associated with a crosslinking reaction of the composition components, which is typically induced, for example, by heat or radiation. Once cured, thermosetting resins will not melt upon heating and are insoluble in solvents.

[0117] Powder coating compositions used with the present invention may also include thermoplastic powder coating compositions. As used herein, the term "thermoplastic" means a composition comprising polymeric components not covalently linked and thus capable of undergoing liquid flow upon heating and soluble in solvents.

[0118] Suitable film-forming resins comprising at least a portion of the binder forming 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 similar terms refer to both acrylates and their corresponding methacrylates. Furthermore, the film-forming resin may have any of a variety of functional groups, including but not limited to carboxylic acid groups, amine groups, epoxy groups, hydroxyl groups, thiol groups, urethane groups, amide groups, urea groups, isocyanate groups (including terminated isocyanate groups), and combinations thereof.

[0119] Thermosetting coating compositions typically include a crosslinking agent, which can be selected from any crosslinking agent known in the art that reacts with the functional groups of one or more film-forming resins used in the powder coating composition. As used herein, the term "crosslinking agent" refers to a molecule containing two or more functional groups that are reactive with other functional groups and capable of linking two or more monomers or polymers by chemical bonds. Alternatively, the film-forming resin of the binder forming the powder coating composition may have self-reactive functional groups; in this way, such resins are self-crosslinked.

[0120] Suitable crosslinking agents include phenolic resins, amino resins, epoxy resins, β-hydroxy(alkyl)amides, alkylated carbamates, (meth)acrylates, isocyanates, blocked isocyanates, polybasic acids, acid anhydrides, organometallic acid-functional materials, polyamines, polyamides, amino plastics, carbodiimides, oxazolines, and combinations thereof.

[0121] The powder coating composition may also be substantially free of, essentially free of, or completely free of any of the film-forming resins and / or crosslinking agents previously described. For example, the powder coating composition may be substantially free of, essentially free of, or completely free of hydroxyl-functionalized film-forming resins and / or isocyanate-functionalized crosslinking agents. Based on the total weight of the powder coating composition, the term “substantially free of” as used in this context means that the powder coating composition contains less than 1,000 parts per million (ppm), “essentially free of” means less than 100 ppm, and “completely free of” means less than 20 parts per billion (ppb) of hydroxyl-functionalized film-forming resins and / or isocyanate-functionalized crosslinking agents.

[0122] The powder coating composition may also contain other optional materials. For example, the powder coating composition may also include a colorant. As used herein, "colorant" means any substance that imparts color and / or other opacity and / or other visual effects to the composition. Colorants may 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 may be used in the coatings of the present invention.

[0123] Colorants include pigments (organic or inorganic), dyes, and colorants, such as those used in the paint industry and / or listed in the Dry Powder Pigment Manufacturers Association (DCMA), as well as special effects compositions. Colorants may comprise, for example, finely ground solid powders that are insoluble but wettable under the conditions of use. Colorants may be organic or inorganic and may be agglomerated or non-agglomerated. Colorants can be incorporated into coatings using abrasive media, such as acrylic abrasive media, the use of which is well known to those skilled in the art.

[0124] Pigments and / or pigment compositions include, but are not limited to, carbazole dioxazine crude pigments, azo, monoazo, diazo, naphthol AS, benzimidazolone, isoindolinone, isoindolin and polycyclic phthalocyanine, quinacridone, perylene, violet ketone, diketopyrrolopyrrole, thioindigo, anthraquinone, indigoanthraquinone, anthraquinone pyrimidine, flavinanthraquinone, pinanthraquinone, anthraquinone, dioxazine, triarylcarbium, quinophthalone pigments, diketopyrrolopyrrole red (“DPPBO Red”), titanium dioxide, carbon black, and mixtures thereof. The terms “pigment” and “colored filler” are used interchangeably.

[0125] Dyes include, but are not limited to, solvent-based dyes and / or water-based dyes, such as phthalocyanine green or phthalocyanine blue, iron oxide, bismuth vanadate, anthraquinone and perylene, and quinacridone.

[0126] Pigments include, but are not limited to, pigments dispersed in water-based or water-miscible carriers, such as AQUA-CHEM 896, which is commercially available from Degussa, Inc., CHARISMA colorants, and MAXITONER industrial colorants, which are commercially available from the Accurate Dispersion division of Eastman Chemical, Inc.

[0127] Other suitable materials that can be used with the coating compositions of the present invention include plasticizers, abrasion-resistant particles, fillers (including but not limited to mica, talc, clay and inorganic minerals), metal oxides, metal flakes, various forms of carbon, antioxidants, hindered amine light stabilizers, UV light absorbers and stabilizers, surfactants, flow and surface control agents, thixotropic agents, catalysts, reaction inhibitors, corrosion inhibitors and other common additives.

[0128] The powder coating composition may also contain an additive containing an oxazolidinone group. For example, the oxazolidinone additive may contain at least two oxazolidinone functional groups. The chemical structure of the additive may also have a linking group separating the two oxazolidinone functional groups. The linking group may be an aromatic group. The additive may also contain two linking groups chemically bonded to the oxazolidinone functional group and the terminal group. The linking group may contain an aromatic group or an aliphatic group. For example, the linking group may contain bisphenol A. The terminal group may contain an epoxy group. The structure of the oxazolidinone additive is shown in Table 2 below:

[0129] Table 2

[0130] Powder-coated oxazolidinone structure

[0131]

[0132] Based on the total weight of the coating composition, the oxazolidinone additive may be present in the coating composition in amounts 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 covered by any two of the foregoing values ​​as endpoints. For example, the oxazolidinone additive may be present in amounts from 0.1 wt.% to 40 wt.%, 0.5 wt.% to 40 wt.%, 1 wt.% to 40 wt.%, 1 wt.% to 30 wt.%, 5 wt.% to 25 wt.%, or 10 wt.% to 20 wt.%.

[0133] The powder coating compositions of the present invention can be applied to a variety of substrates. Therefore, this disclosure further relates to a substrate which is at least partially coated with a coating deposited by the powder coating compositions described herein. It should be understood that the powder coating compositions can be applied to the substrate as a single coating or as a coating in a multilayer coating composite.

[0134] The components of a powder coating composition can be contacted by mixing, grinding, or any suitable contact method. The components may be solids at room temperature (23°C), and more specifically, may be powders with an average particle size. Individual components may be contacted in any suitable ratio to form a coating composition.

[0135] Before applying the coating composition, the substrate can be preheated to a surface temperature or overall temperature. The substrate can be heated to surface temperatures as low as 100℉, 125℉, 150℉, 175℉, 200℉ or as high as 225℉, 250℉, 275℉, 300℉, 325℉, 350℉, 375℉, 400℉ or any range including any two of these values ​​as endpoints. In other words, the substrate can be heated to surface temperatures as low as 40℃, 50℃, 60℃, 70℃, 80℃, 90℃, 100℃, 110℃ or as high as 120℃, 130℃, 140℃, 150℃, 160℃, 170℃, 180℃, 190℃, 200℃, 210℃ or any range including any two of these values ​​as endpoints. The substrate can be heated to surface temperatures of 40°C to 150°C, 50°C to 150°C, 60°C to 150°C, 70°C to 150°C, 80°C to 150°C, 90°C to 150°C, 100°C to 150°C, 110°C to 150°C, 110°C to 140°C, or 120°C to 140°C.

[0136] Once the coating composition has been applied to the substrate, the coating is cured. Curable coating compositions can be cured by heating, increasing or decreasing pressure, chemical methods such as by moisture, or by other means such as photochemical radiation and combinations thereof. Curing may involve an initial curing step utilizing radiation, followed by heating. The term "photochemical radiation" refers to electromagnetic radiation that can initiate a chemical reaction. Photochemical radiation includes, but is not limited to, visible light, ultraviolet (UV) radiation, infrared (IR) radiation, X-rays, and gamma radiation.

[0137] The coating composition can be cured at low temperatures. Specifically, the coating composition can be cured at temperatures below 450℉, below 425℉, below 400℉, below 375℉, below 350℉, below 325℉, below 300℉, below 290℉, below 280℉, below 275℉, below 270℉, below 260℉, below 250℉, or any range including any two of these values ​​as endpoints. In other words, the coating composition can be cured at temperatures below 240℃, below 230℃, below 220℃, below 210℃, below 200℃, below 190℃, below 180℃, below 170℃, below 160℃, below 150℃, below 140℃, below 130℃, below 120℃, or any range including any two of these values ​​as endpoints. The coating composition can be cured at temperatures of 120°C to 200°C, 120°C to 190°C, 120°C to 180°C, 120°C to 170°C, 120°C to 160°C, 120°C to 150°C, 120°C to 140°C, or 120°C to 130°C.

[0138] The curing step can be performed for any suitable time to allow the coating to fully or at least partially cure. Curing time can vary depending on the substrate, coating composition, coating thickness, environmental conditions, curing method, or any combination of these factors. Curing times can be as short as 1 minute, 2 minutes, 3 minutes, 4 minutes, 5 minutes, 6 minutes, 7 minutes, 8 minutes, 9 minutes, 10 minutes, or as long 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. Curing times can be from 1 minute to 30 minutes, 1 minute to 20 minutes, 1 minute to 15 minutes, 1 minute to 10 minutes, 1 minute to 6 minutes, 5 minutes to 15 minutes, 5 minutes to 10 minutes, or 3 minutes to 9 minutes.

[0139] The thickness of the entire coating on the substrate can be as small as 0.1 mil, 0.2 mil, 0.3 mil, 0.4 mil, 0.5 mil, 0.6 mil, 0.7 mil, 0.8 mil, 0.9 mil, 1 mil, 1.5 mil, 2 mil, 2.5 mil or as large as 20 mil, 15 mil, 14 mil, 13 mil, 12 mil, 11 mil, 10 mil, 9 mil, 8 mil, 7 mil, 6 mil, 5 mil, 4 mil, 3.9 mil, 3.8 mil, 3.7 mil, 3.6 mil, 3.5 mil, 3.4 mil, 3.3 mil, 3.2 mil, 3.1 mil, 3 mil, or any range including any two of these amounts as endpoints. The thickness of the entire coating can be 1 mil to 4 mil, 1.5 mil to 2.5 mil, or 2 mil to 3 mil. The thickness can be measured according to ASTM D7091-13 test method and an Elcometer 415 B double FNF film measuring instrument.

[0140] Other application methods that can be used to apply the coating composition to a substrate include: spraying, such as incorporating the coating composition into a liquid formulation and using a spraying device; wiping, wherein the coating composition is contained on and / or in a wiping material and is wiped manually or automatically; sandblasting, wherein the coating composition is solid and is sandblasted onto the substrate surface; electrostatic application as a powder; brushing or rolling the coating composition onto the substrate, such as by incorporating the coating composition into a brushable or rollable formulation (e.g., a liquid or gel); vapor deposition; electrodeposition, wherein the formulation is liquid and electrophoretic coating is performed; or any combination thereof. The coating composition can also be applied in-mold during extrusion, calendering, or other processing of the substrate material.

[0141] The coating composition can be applied directly to the substrate without any intermediate layer between the coating composition and the substrate. The coating composition can be applied directly to the metal substrate before or after cleaning and / or treating the substrate as further described herein, but before applying any coating. The coating composition can also be applied during cleaning, such as with a cleaning agent. The coating composition can be applied to the entire surface, edges, and corners of the substrate, or it can be applied to selected portions of the substrate.

[0142] The coating composition can also form a continuous or semi-continuous layer on a substrate, or it can be applied to certain points / areas of the substrate, such as edges and corners. As used herein, the area referred to as an "edge" will vary depending on the specific substrate, but may include, for example, the outermost surface of the substrate.

[0143] The coating composition can be applied as a single layer to an uncoated substrate. For example, the coating composition can be applied to the substrate to form a single coating. As used herein, "single coating" refers to a single coating without any additional coating. Therefore, the coating composition can be applied directly to the substrate and cured to form a single coating, i.e., a single layer.

[0144] The coated substrate of this disclosure may further comprise one or more additional coatings, such as a second outer coating deposited onto at least a portion of the first coating composition, to form a multilayer coating, as by applying a topcoat. When forming a multilayer coating, the first coating composition may be cured before applying the additional outer coatings, or one or more of the additional outer coatings and the first coating composition may be cured simultaneously. It should be understood that the second outer coating and the additional outer coatings may be in solid or liquid form. The coating composition may be layered under a topcoat or a series of topcoats to form a stack. The coating composition may be a first layer applied as a base coat or primer to a bare substrate. The primer may then have subsequent layers applied on top of it to form a multilayer coating.

[0145] The powder-coated articles envisioned in this disclosure can have low scribing creep as measured according to ASTM B117-19. For example, the coated articles can have scribing 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 covered by any two of the foregoing values ​​as endpoints. For example, powder-coated articles can have scribing creep of 1% to 60%, 10% to 50%, or 20% to 40%.

[0146] Powder-coated articles can also have dimensions 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 Strike creep of mm or less, 1 mm or less, or any range covered by any two of the foregoing values ​​as endpoints. For example, powder-coated articles may have strike creep of 1 mm to 10 mm.

[0147] Once cured on top of the article, the coating can be thermally conductive. For example, the coating can have a thermal conductivity of at least 0.3 W / mK as measured according to ASTM D7984, such as at least 0.5 W / mK, such as at least 0.7 W / mK, such as at least 0.9 W / mK, such as at least 1.5 W / mK, or higher.

[0148] When exposed to UV light, the powder-coated articles contemplated in this disclosure may exhibit minor changes in gloss or color. They can be subjected to accelerated aging exposure testing according to SAE J2527 or SAE J2020 UVA to simulate outdoor sunlight exposure on an accelerated basis.

[0149] V. Liquid Coating Composition

[0150] Liquid polymer coating compositions are typically applied to substrates, particularly metallic substrates, to protect them from degradation, enhance their appearance (e.g., provide color, brightness, etc.), and / or reflect light. Many such polymer coating compositions are applied to planar substrates (e.g., using roll-to-roll coating processes), which subsequently form finished articles.

[0151] This disclosure provides a liquid coating composition comprising a polyester resin and an additive containing an oxazolidinone functional group. The liquid coating composition may also optionally contain a curing agent.

[0152] Polyesters that can be used as resins in this disclosure and methods for their preparation are well known in the art. Polyesters can be prepared from polycarboxylic acids or their esterifiable derivatives, as well as from polyols, by any suitable known method. Regarding the polyols that can be used in practicing this invention, they can include any material containing reactive hydrogen atoms and reacting with isocyanate or isocyanurate groups. These materials include hydroxyl-functional acrylics, hydroxyl-functional polyesters, hydroxyl-functional polyethers, polyamines, polyamides, short-oil alkyd resins, castor oil, epoxy resins having secondary hydroxyl groups, phenolic resins, and hydroxyl-functional vinyl resins. Vinyl resins can be used to promote adhesion if desired.

[0153] Suitable polyhydroxy alcohols include ethylene glycol, propylene glycol, butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, glycerol, trimethylolpropane, and pentaerythritol. 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.

[0154] To facilitate the crosslinking of the film-forming resin, the liquid coating composition according to this disclosure may further include a crosslinking agent. The crosslinking agent may be, for example, an isocyanate crosslinking agent.

[0155] Regarding the isocyanates that can be used, they can be divided into four different categories. The four categories include diphenylmethane 4,4'-diisocyanate (MDI), toluene diisocyanate (TDI), isophorone diisocyanate (IPDI), and hexamethylene diisocyanate (HDI).

[0156] HDI-based polyisocyanates represent an important class of polyisocyanates used in polyurethane coatings. Specifically, coatings prepared using HDI-based products typically exhibit additional chemical and abrasion resistance. They also tend to exhibit desired weathering characteristics, including gloss retention, as well as resistance to yellowing and chalking.

[0157] BAYER's Desmodur N-75, Desmodur N-100, and Desmodur N-3200 are commercially known HDI-based polyisocyanates. They are polymeric materials containing biuret groups. HDI can be converted into trimers containing isocyanurate rings. These products are commercially available from BAYER under the trade names Desmodur N-3300 and Desmodur N-3390.

[0158] The liquid coating composition may also include any suitable solvent. Suitable solvents include aromatic hydrocarbons, such as toluene, xylene, and ketones, such as methyl ethyl ketone and methyl isobutyl ketone, methyl isopentyl ketone (MIAK), methyl amyl ketone (MAK), methyl ether propylene glycol acetate, and combinations thereof.

[0159] Liquid coating compositions may also contain pigments or colorants to alter the visual appearance of the coating. Colorants may be organic or inorganic dyes and pigments, such as those used in the paint industry and / or listed in the Dry Powder Pigment Manufacturers Association (DCMA), as well as special effects compositions. Colorants may comprise finely granulated solid powders that are insoluble but wettable under the conditions of use. Colorants may be organic or inorganic and may be agglomerated or non-agglomerated. Colorants can be incorporated into the coating using abrasive media such as acrylic abrasive media, the use of which is well known to those skilled in the art. Colorants and / or colorant compositions may include, but are not limited to, carbazole dioxazine crude pigments, azo, monoazo, diazo, naphthol AS, benzimidazolone, isoindolinone, isoindolin and polycyclic phthalocyanine, quinacridone, perylene, violet ketone, diketopyrrolopyrrole, thioindigo, anthraquinone, indigoanthraquinone, anthraquinone pyrimidine, flavinthrone, pinantrone, anthraquinone, dioxazine, triarylcarbium, quinacridone pigments, diketopyrrolopyrrole red (“DPPBO Red”), titanium dioxide, carbon black, and mixtures thereof. Colorants may also include, but are not limited to, solvent-based dyes and / or water-based dyes, such as phthalocyanine green or phthalocyanine blue, iron oxide, bismuth vanadate, anthraquinone and perylene, and quinacridone.

[0160] The liquid coating composition may further optionally include a flow control agent, sometimes referred to as a leveling agent, for promoting the formation of a continuous and uniform coating. Suitable flow control agents include polyacrylates, nonionic fluorinated alkyl ester surfactants, nonionic alkyl aryl polyether alcohols, silicones, etc., and combinations comprising at least two of the aforementioned flow control agents. Flow control agents are typically converted into a liquid in powder form at room temperature by adsorption onto silica-based materials. One flow control agent is a 2-ethyl acrylate polymer acrylic resin, available from Estron Chemical, Inc. under the trade name RESIFLOW® P-67; and a 2-hydroxy-1,2-diphenyl ethyl ketone crystalline solid, considered to keep the molten coating open for a suitable time to allow degassing before the formation of a hardened film, sold by DSM, Inc. under the trade name Benzoin. The liquid coating composition may also include a drying flow agent, such as fumed silica or colloidal alumina, such as those sold by Evonik Corporation under the trade name AEROSIL®.

[0161] The liquid coating composition may also contain additives comprising oxazolidinone groups. For example, the oxazolidinone additive may contain at least two oxazolidinone functional groups. Both oxazolidinone functional groups may be bonded to a single linking group. The oxazolidinone functional groups may also be bonded to at least two linking groups bonded to terminal groups. The linking groups may include aromatic or aliphatic groups, and the terminal groups may include epoxy groups, acid groups, hydroxyl groups, amine groups, aromatic groups, or aliphatic groups.

[0162] Oxazolidinone additives can have a main chain structure containing poly-THF.

[0163] The structures of oxazolidinone additives are shown in Table 3 below:

[0164] Table 3

[0165] Liquid-coated oxazolidinone structure

[0166]

[0167] Oxazolidinone additives may be present in liquid coating compositions in amounts 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 in any range covered by any two of the foregoing values ​​as endpoints. For example, oxazolidinone additives may be present in amounts 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.%.

[0168] The liquid coating compositions of the present invention can be applied to a variety of substrates. Therefore, this disclosure further relates to a substrate which is at least partially coated with a coating deposited from the liquid coating compositions described herein. Suitable substrates include steel and coated steel, such as iron phosphate pretreated steel and zirconium pretreated steel.

[0169] The coating composition can be applied as a single layer to an uncoated substrate. For example, the coating composition can be applied to the substrate to form a single coating. As used herein, "single coating" refers to a single coating without any additional coating. Therefore, the coating composition can be applied directly to the substrate and cured to form a single coating, i.e., a single layer.

[0170] The coated substrate of this disclosure may further comprise one or more additional coatings, such as a second outer coating deposited onto at least a portion of the first coating composition, to form a multilayer coating, as by applying a topcoat. When forming a multilayer coating, the first coating composition may be cured before applying the additional outer coatings, or one or more of the additional outer coatings and the first coating composition may be cured simultaneously. It should be understood that the second outer coating and the additional outer coatings may be in solid or liquid form. The coating composition may be layered under a topcoat or a series of topcoats to form a stack. The coating composition may be a first layer applied as a base coat or primer to a bare substrate. The primer may then have subsequent layers applied on top of it to form a multilayer coating.

[0171] The liquid-coated articles envisioned in this disclosure can have low scribing creep as measured according to ASTM B117-19. For example, the coated articles can have scribing 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%.

[0172] Additionally, compared to articles coated with the same oxazolidinone-free coating, liquid-coated articles may have a reduction in scribing creep of at least 10% according to ASTM B117-19. For example, the reduction in scribing 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%.

[0173] VI. Packaging Coating Composition

[0174] Various coatings are used to coat the surfaces of packaging containers. Packaging containers are available in a variety of configurations to suit a wide range of end-uses and products. The inner surfaces of metal packaging containers are typically coated with one or more layers to prevent inappropriate interactions between the metal substrate and the components of the packaged product, which could lead to corrosion of the metal substrate and / or contamination of the packaged product.

[0175] This disclosure provides a packaging coating composition comprising a polyester resin, an acrylic-modified polyester, or an acrylic resin (latex); and an additive comprising an oxazolidinone functional group. The packaging coating composition may also include an optional curing agent.

[0176] The film-forming resin of the packaging coating composition can be a polyester resin. Polyesters that can be used as resins in this disclosure and methods for their preparation are well known in the art. Polyesters can be prepared from polycarboxylic acids or their esterifiable derivatives, as well as from polyols by any suitable known method. Regarding the polyols that can be used in practicing this invention, they can include any material containing reactive hydrogen atoms and reacting with isocyanate or isocyanurate groups, melamine, phenols, or benzoguanamines. These materials include hydroxyl-functional acrylics, hydroxyl-functional polyesters, hydroxyl-functional polyethers, polyamines, polyamides, short-oil alkyd resins, castor oil, epoxy resins having secondary hydroxyl groups, phenolic resins, and hydroxyl-functional vinyl resins. Vinyl resins can be used to promote adhesion if desired.

[0177] Polyester materials can be formed from any suitable polybasic acid. Suitable polycarboxylic acids include, but are not limited to, the following: maleic acid; fumaric acid; itaconic acid; adipic acid; azelaic acid; succinic acid; sebacic acid; glutaric acid; sebacic acid; dodecanoic acid; phthalic acid; isophthalic acid; 5-tert-butylisophthalic acid; tetrachlorophthalic acid; tetrahydrophthalic acid; trimellitic acid; naphthalenedicarboxylic acid; naphthalenetetracarboxylic acid; terephthalic acid; hexahydrophthalic acid; methylhexahydrophthalic acid; dimethyl terephthalate; cyclohexanedicarboxylic acid; chlorobenzyl anhydride; 1,3-cyclohexanedicarboxylic acid; 1,4-cyclohexanedicarboxylic acid; tricyclodecane polycarboxylic acid; inner methylenetetrahydrophthalic acid; inner ethylhexahydrophthalic acid; cyclohexanetetracarboxylic acid; cyclobutanetetracarboxylic acid; acidic monomers having an aliphatic group containing at least 15 carbon atoms; esters and anhydrides of all the above acids, and combinations thereof.

[0178] Suitable for use, the carboxylic acid group of a polybasic acid can be linked by an aryl bridging group. Therefore, suitable for use, polybasic acids can include aromatic polybasic acids.

[0179] The polybasic acid components may include: terephthalic acid (TPA), isophthalic acid (IPA), dimethyl terephthalate, dimethyl isophthalic acid, 1,4-cyclohexanedicarboxylic acid, hexahydrophthalic anhydride, 2,6-naphthalenedicarboxylic acid, adipic acid, phthalic anhydride, maleic anhydride and / or fumaric anhydride.

[0180] Polyester materials can be formed from diacids. Polyester materials can be formed from any suitable diacid. Suitable diacids include, but are not limited to, the following: phthalic acid; isophthalic acid; terephthalic acid; 1,4-cyclohexanedicarboxylic acid; succinic acid; adipic acid; azelaic acid; sebacic acid; fumaric acid; 2,6-naphthalenedicarboxylic acid; phthalic acid; phthalic anhydride; tetrahydrophthalic anhydride; maleic anhydride; succinic anhydride; itaconic anhydride; diester materials, such as dimethyl ester derivatives, such as dimethyl isophthalate, dimethyl terephthalate, dimethyl 1,4-cyclohexanedicarboxylic acid, dimethyl 2,6-naphthalenedicarboxylic acid, dimethyl fumarate, dimethyl phthalate, dimethyl succinate, dimethyl glutarate, dimethyl adipate; acidic monomers having an aliphatic group containing at least 15 carbon atoms; esters and anhydrides of all the above acids; and mixtures thereof.

[0181] As used herein, “polyol” and similar terms refer to compounds having two or more hydroxyl groups, such as two, three, or four hydroxyl groups. The hydroxyl groups of a polyol can be linked by bridging groups selected from: alkylene; alkenylene; ynylene; aryynylene; arylarylene; or arylene. Suitable polyols are organic polyols.

[0182] Polyester materials can 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; hexanediol; polyethylene glycol; polypropylene glycol and neopentyl glycol; hydrogenated bisphenol A; cyclohexanediol; propylene glycol, including 1,2-propanediol; 1,3-propanediol; butyl ethyl propylene glycol; 2-methyl-1,3-propanediol; and 2-ethyl-2-butyl-1,3-propanediol; butanediol, 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. - Cyclobutanediol; and 2-ethyl-1,4-butanediol; pentanediol, including trimethylpentanediol and 2-methylpentanediol; cyclohexanediol; hexanediol, including 1,6-hexanediol; caprolactone diol (e.g., the reaction product of ε-caprolactone and ethylene glycol); hydroxyalkylated bisphenols; polyether diols, such as poly(oxytetramethylene)diol; trimethylolpropane; pentaerythritol; dipentaerythritol; trimethylolethane; trimethylolbutane; dimethylolcyclohexane; bio-derived polyols, such as glycerol, sorbitol; and / or acidic monomers having an aliphatic group having at least 15 carbon atoms, or combinations thereof.

[0183] The film-forming resin in the packaging coating composition can also be an acrylic-modified polyester resin. The acrylic-polyester resin can be obtained by grafting an acrylic polymer and a polyester resin, wherein the polyester resin can be obtained by polymerizing: i) a polyacid component and ii) a polyol component, and wherein one of the polyacid component or the polyol component contains a functional monomer operable to impart functional groups to the polyester resin, such that the acrylic polymer can be grafted onto the polyester resin using said functional groups.

[0184] The polyacid or polyol component of the acrylic polyester resin includes functional monomers operable to impart functional groups to the polyester resin. These functional groups enable the acrylic polymer to be grafted onto the polyester resin using said functional groups. Functionality can include olefinic unsaturation, carboxylic acid functionality, or epoxy functionality. The functional groups can be in the main chain of the polyester resin or in the resulting side chains.

[0185] Functional monomers may include olefinically unsaturated monomers operable to impart olefinically unsaturated functionality to the main chain or derived side chains of a polyester resin. Functional groups may include olefinically unsaturated groups, which may be present in the main chain of the polyester resin. Suitable functional monomers include: maleic acid, maleic anhydride, fumaric acid, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid, aconitic acid, aconitic anhydride, oxaloyl maleic acid, oxaloyl maleic anhydride, mesoconic acid, mesoconic anhydride, phenylmaleic acid, phenylmaleic anhydride, tert-butylmaleic acid, tert-butylmaleic anhydride, monomethyl fumarate, monobutyl fumarate, nadic acid, nadic anhydride, methylmaleic acid, methylmaleic anhydride, and / or trimethylolpropane monoallyl ether.

[0186] When the functional monomer contains a polybasic acid, the functional monomer may be present in an amount of 0.5 to 10 wt.%, such as 1 to 5 wt.%, based on the solid weight of the polybasic acid component.

[0187] When the functional monomer contains a polyol, the functional monomer may be present in an amount of 0.5 to 10 wt.%, such as 1 to 5 wt.%, based on the solid weight of the polyol component.

[0188] The functional monomers of acrylic polyester resins may include maleic acid, maleic anhydride, and / or fumaric acid.

[0189] Acrylic polyester resins can be modified with acrylic acid by grafting acrylic acid-modified polymers onto the polyester resin. This grafting can occur through free radical polymerization, such as through free radical polymerization of olefinic unsaturated polymers onto polyester materials.

[0190] Acrylic-modified polymers can be the acrylic monomers formed. Acrylic-modified polymers can be grafted onto polyester resins by polymerizing acrylic monomers in the presence of polyester materials to form acrylic polyester resins.

[0191] Various acrylic monomers can be combined to prepare acrylic-modified polymers. Suitable monomers include methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate; allyl methacrylate; isobornyl methacrylate, hydroxyethyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid, dimethylaminoethyl methacrylate, butylaminoethyl methacrylate, and / or HEMA phosphates (such as ethylene glycol methacrylate phosphate). Any other acrylic monomers known to those skilled in the art may also be used.

[0192] The term "(meth)acrylate" and similar terms are used by convention and in this document refer to both methacrylate and acrylate.

[0193] Suitable acrylic modified polymers are formed from monomers comprising: methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, methacrylic acid, cyclohexyl methacrylate, allyl methacrylate, dimethylaminoethyl methacrylate, butylaminoethyl methacrylate, and / or HEMA phosphates (such as ethylene glycol methacrylate phosphate).

[0194] Acrylic monomers may contain a ratio of methacrylate monomers to acrylate monomers of at least 1:1, such as at least 2:1, at least 3:1, at least 4:1, or such as at least 5:1. Acrylic monomers may be substantially free of acrylate monomers. The terms "methacrylate monomers" and "acrylate monomers" in the acrylic monomers of the acrylic modified polymer refer to the ratio of the total number of methacrylate monomers to the total number of acrylate monomers among all types of acrylic monomers forming the acrylic modified polymer. For example, if the acrylic modified polymer is formed from methyl methacrylate, methyl acrylate, and butyl acrylate, the ratio of the amount of methyl methacrylate to the combined amount of methyl acrylate and butyl acrylate will be at least 5:1.

[0195] Acrylic monomers may include hydroxyl-functional monomers, such as hydroxyethyl (meth)acrylate. Hydroxyl-functional monomers may be present in amounts of 5 to 40 wt.%, such as 5 to 30 wt.%, or 10 to 20 wt.%, based on the solid weight of the acrylic modified polymer.

[0196] Acrylic-modified polymers may also contain a certain amount (such as 0 to 30 wt.% by solid weight of the acrylic-modified polymer) of non-acrylic monomers. Such non-acrylic monomers may include other olefinically unsaturated monomers, such as styrene, ethylene, propylene, vinyltoluene, butadiene, 1-octene or isoprene, vinyl esters (such as vinyl acetate), and / or acrylic monomers (such as (meth)acrylonitrile).

[0197] It has been determined that acrylic-modified polymers may contain methacrylic acid or acrylic acid to impart acid functionality to the acrylic-modified polymers. The acid functional groups on the acrylic-modified polymers can be at least partially neutralized with a neutralizing agent.

[0198] The Tg of acrylic-modified polymers (which is a measure of the Tg of acrylic-modified polymers as simple acrylic polymers polymerized without polyester resin (or grafted onto polyester resin)) can range from 20°C to 120°C. The Tg of acrylic-modified polymers can be calculated using the Fox equation, as provided in “Coatings of Polymers and Plastics”, Ryntz RA and Yaneff PV, CRC Press, February 4, 2003, page 134.

[0199] Suitable neutralizing agents contain ammonia or amine functional groups: methylethanolamine, dimethylethanolamine (DMEA), trimethylamine, and diethylenetriamine.

[0200] The acid functional groups on the acrylic-modified polymer can be neutralized by at least 30% with a neutralizing agent. The acid functional groups on the acrylic-modified polymer can be neutralized by at least 50% with a neutralizing agent. The acid functional groups on the acrylic-modified polymer can be neutralized by at least 75% with a neutralizing agent.

[0201] The packaging coating composition may also contain a crosslinking material. The coating composition may include any suitable crosslinking material. Suitable crosslinking materials will be well known to those skilled in the art.

[0202] Crosslinking materials can be used to crosslink polyester materials. Crosslinking materials can be monomers, dimers, oligomers, (co)polymers, or mixtures thereof. Crosslinking materials can be dimers or trimers.

[0203] Suitable crosslinking materials include, but are not limited to: phenolic resins (or phenol-formaldehyde resins); amino plastic resins (or triazine-formaldehyde resins); amino resins; epoxy resins; isocyanate resins; β-hydroxy(alkyl)amide resins; alkylated urethane resins; polybasic acids; acid anhydrides; organometallic acid-functional materials; polyamines; and / or polyamides and combinations thereof.

[0204] Suitable phenolic resins are formed by reacting phenol with aldehydes or ketones, such as by reacting phenol with aldehydes, such as by reacting phenol with formaldehyde or acetaldehyde, or even by reacting phenol with formaldehyde. Suitable phenols that can be used to form phenolic resins are phenol, butylphenol, xylenol, and cresol. The general preparation of phenolic resins is described in "The Chemistry and Application of Phenolic Resins or Phenoplasts", Volume V, Part I, edited by Dr. Oldring; John Wiley and Sons / Cita Technology Limited, London, 1997. Phenolic resins can be of the methyl phenolic resin type. "Methyl phenolic resin type" refers to resins formed in the presence of an alkaline (basic) catalyst and optionally excess formaldehyde. Suitable commercially available phenolic resins include, but are not limited to, those available from Allnex under the trade name PHENODUR (RTM), such as PHENODUR EK-827, PHENODUR VPR1785, PHENODUR PR 515, PHENODUR PR516, PHENODUR PR 517, PHENODUR PR 285, PHENODUR PR612, or PHENODUR PH2024; resins available from Sumitomo Bakelite co., ltd. under the trade name BAKELITE (RTM), such as BAKELITE 6582 LB, BAKELITE 6535, BAKELITE PF9989, or BAKELITE PF6581; SFC 112 available from the SI Group; DUREZ (RTM) 33356 available from SHHPP; and ARALINK (RTM) available from Bitrez. 40-852; or combinations thereof.

[0205] Suitable isocyanate resins include, but are not limited to, the following: isophorone diisocyanates (IPDI), such as those available from Covestro under the trade name DESMODUR (RTM), e.g., DESMODUR VP-LS 2078 / 2 or DESMODUR PL 340; or those available from Evonik under the trade name VESTANAT (RTM), e.g., VESTANAT B 1370, VESTANAT B 118 6A, or VESTANAT B 1358 A; blocked aliphatic polyisocyanates based on hexamethylene diisocyanate (HDI), such as those available from Covestro under the trade name DESMODUR (RTM), e.g., DESMODUR BL3370 or DESMODUR BL 3175 SN; those available from Asahi KASEI under the trade name DURANATE (RTM), e.g., DURANATE MF-K60X; and those available from Vencorex. Chemicals commercially acquires those sold under the trade name TOLONATE (RTM), such as TOLONATE D2, or those sold under the trade name TRIXENE (RTM), such as TRIXENE-BI-7984 or TRIXENE 7981, which are available from Baxenden; or combinations thereof.

[0206] Crosslinked materials may contain nitrogen. Crosslinked materials may be in the form of amines or amides. Crosslinked materials may contain hydroxyl-substituted amines or amides.

[0207] Crosslinked materials may include hydroxyalkylamide materials, such as β-hydroxyalkylamide materials.

[0208] Crosslinking materials may include commercially available β-hydroxyalkylamide crosslinking materials, such as PRIMID XL-552 (available from EMS); PRIMID QM-1260 (available from EMS Chemie); and N,N,N',N'-tetratetra(2-hydroxypropyl)hexamethylenediamide.

[0209] Crosslinked materials can be in the form of urea materials. Crosslinked materials can contain hydroxyl-substituted urea materials. Crosslinked materials can contain hydroxyl-functionalized alkyl polyurea materials.

[0210] Hydroxyl-functionalized alkyl polyurea materials may include materials according to formula (I):

[0211]

[0212] R comprises an isocyanurate moiety, a biuret moiety, a urethane moiety, a glycourea moiety, a benzoguanamine moiety, a polyetheramine moiety, and / or a polymer moiety different from a polyetheramine and having a Mn of 500 or greater; wherein each R1 is independently hydrogen, an alkyl group having carbon, or a hydroxyl-functionalized alkyl group having two or more carbons, and at least one R1 is a hydroxyl-functionalized alkyl group having two or more carbons; and n is 2-6.

[0213] Hydroxyl-functionalized alkyl polyurea materials may include materials according to formula (II):

[0214]

[0215] Wherein R2 is a substituted or unsubstituted C1 to C36 alkyl group, aromatic group, isocyanurate moiety, biuret moiety, urethane moiety, glycourea moiety, benzoguanamine moiety, polyetheramine moiety and / or a polymer moiety different from polyetheramine and having Mn of 500 or greater; wherein each R1 is independently hydrogen, an alkyl group having carbon or a hydroxyfunctional alkyl group having two or more carbons, and at least one R1 is a hydroxyfunctional alkyl group having two or more carbons; and n is 2-6.

[0216] Further details of suitable hydroxyl-functionalized alkyl polyurea materials are disclosed in PCT patent application WO 2017 / 123955, the entire contents of which are incorporated herein by reference.

[0217] Suitable amino plastic resins include those that are reaction products of reaction mixtures comprising triazine such as melamine or benzoguanidine and formaldehyde. These condensates can typically be etherified with methanol, ethanol, butanol, or mixtures thereof. For the chemistry, preparation, and use of amino plastic resins, see “The Chemistry and Applications of Amino Crosslinking agents or Aminoplast”, Volume V, Part 11, p. 21ff., edited by Dr. Oldring; John Wiley & Sons / Cita Technology Limited, London, 1998. Suitable commercially available amino plastic resins include, but are not limited to, those sold under the trade name MAPRENAL (registered trademark), such as MAPRENAL MF980 (available from Prefere Resins); those sold under the trade name CYMEL (registered trademark), such as CYMEL 303 and CYMEL 1128 (available from Allnex Industries); and combinations thereof.

[0218] Crosslinked materials may include materials according to formula (III)

[0219]

[0220] R1 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; 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 alkylaryl (such as C5 to C25 alkylaryl); at least one of R2 to R5, or R2 to R7 (when present), is -CHR8OR9, for example, all R2 to R5, or R2 to R7 (when present), can be -CHR8OR9.

[0221] In the crosslinked material according to formula (III), R1 can be C1 to C20 alkyl, C4 to C24 aryl, C5 to C25 aryl or -NR6R7; such as C4 to C24 aryl or C5 to C25 aryl, or C4 to C24 aryl, such as C4 to C12 aryl, such as C5 aryl.

[0222] In the crosslinked material according to formula (III), R1 can be -NR6R7.

[0223] In the crosslinked material according to formula (III), R2 to R7 (when appropriately present) may each independently be 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.

[0224] In the crosslinked material according to formula (III), R2 to R7 (where suitably present) may each independently be 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 Cs alkyl, or -CHR8OR9, such as -CHR8OR9, and Rs may independently be hydrogen, C1 to C20 alkyl, C4 to C24 aryl, C5 to C25 aralkyl, alkoxyalkyl C2 to C40 alkoxyalkyl or C5 to C25 alkylaryl, such as hydrogen, C1 to C20 alkyl, such as hydrogen; and Rg can be hydrogen, C1 to C20 alkyl, C4 to C24 aryl, Cs to C25 aralkyl, alkoxyalkyl C2 to C40 alkoxyalkyl or Cs to C25 alkylaryl; 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.

[0225] The crosslinking material according to formula (III) can be the reaction product of a reaction mixture comprising triazine such as melamine or benzoguanamine and formaldehyde. These condensates can typically be etherified with methanol, ethanol, butanol, or mixtures thereof. For the chemistry, preparation, and use of amino plastic resins, see “The Chemistry and Applications of AminoCrosslinking agents or Aminoplast”, Volume V, Part 11, p. 21ff., edited by Dr. Oldring; John Wiley & Sons / Cita Technology Limited, London, 1998.

[0226] The crosslinking material according to formula (III) may include melamine or its derivatives, such as butylated and / or methylated melamine; and / or benzoguanamine or its derivatives, such as butylated and / or methylated benzoguanamine. The crosslinking material according to formula (III) may include benzoguanamine or its derivatives, such as butylated and / or methylated benzoguanamine.

[0227] Crosslinking materials may include those that are reaction products comprising a reaction mixture of triazine, such as melamine or benzoguanamine, and formaldehyde. Crosslinking materials may include benzoguanamine or derivatives thereof.

[0228] Benzoguanidine or its derivatives may include commercially available benzoguanidine or its derivatives. Suitable commercially available benzoguanidine and its derivatives include, but are not limited to: benzoguanidine-formaldehyde-based materials, such as those sold under the trade name CYMEL (registered trademark), such as CYMEL 1123 (available from Allnex Industries), those sold under the trade name ITAMIN (registered trademark), such as ITAMIN BG143 (available from Galstaff Multiresine), or those sold under the trade name MAPRENAL (registered trademark), such as MAPRENAL BF892 and MAPRENAL BF 892 / 68B (available from Prefere Resins); glycourea-based materials, such as those sold under the trade name CYMEL (registered trademark), such as CYMEL 1170 and CYMEL 1172 (available from Allnex); and combinations thereof.

[0229] Crosslinking materials can be present in the coating composition in any suitable amount.

[0230] Based on the total solid weight of the coating composition, the coating composition may contain at least 0.5 wt.% of crosslinking material, such as at least 1 wt.%, at least 5 wt.%, at least 10 wt.%, or at least 15 wt.% of crosslinking material based on the total solid weight of the coating composition.

[0231] Based on the total solid weight of the coating composition, the coating composition may contain 0.5 to 90 wt.% or 1 to 90 wt.%, such as 1 to 80 wt.%, such as 1 to 70 wt.%, such as 1 to 60 wt.%, such as 1 to 50 wt.%, such as 1 to 40 wt.%, such as 1 to 30 wt.%, or even 1 to 25 wt.% of crosslinking material. Based on the total solid weight of the coating composition, the coating composition may contain 5 to 90 wt.%, such as 5 to 80 wt.%, such as 5 to 70 wt.%, such as 5 to 60 wt.%, such as 5 to 50 wt.%, such as 5 to 40 wt.%, such as 5 to 30 wt.%, or even 5 to 25 wt.% of crosslinking material. Based on the total solid weight of the coating composition, the coating composition may contain 10 to 90 wt.%, such as 10 to 80 wt.%, such as 10 to 70 wt.%, such as 10 to 60 wt.%, such as 10 to 50 wt.%, such as 10 to 40 wt.%, such as 10 to 30 wt.%, or even 10 to 25 wt.% or 10 to 20 wt.% of crosslinking material. Based on the total solid weight of the coating composition, the coating composition may contain 15 to 90 wt.%, such as 15 to 80 wt.%, such as 15 to 70 wt.%, such as 15 to 60 wt.%, such as 15 to 50 wt.%, such as 15 to 40 wt.%, such as 15 to 30 wt.%, or even 15 to 25 wt.% of crosslinking material.

[0232] The packaging coating composition may also contain additives containing oxazolidinone groups. For example, the oxazolidinone additive may contain at least two oxazolidinone functional groups. Both oxazolidinone functional groups may be bonded to a single linking group. The oxazolidinone functional groups may also be bonded to at least two linking groups bonded to terminal groups. The linking groups may include aromatic or aliphatic groups, and the terminal groups may include epoxy groups, acid groups, hydroxyl groups, amine groups, aromatic groups, or aliphatic groups. The structures of the oxazolidinone additives are shown in Table 4 below:

[0233] Table 4

[0234] Packaging coating oxazolidinone structure

[0235]

[0236] Based on the total weight of the packaging coating composition, the oxazolidinone additive may be present in the packaging coating composition in amounts 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 in any range covered by any two of the foregoing values ​​as endpoints. For example, oxazolidinone additives may be present in amounts of 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.%.

[0237] The coating composition can be applied as a single layer to an uncoated substrate. For example, the coating composition can be applied to the substrate to form a single coating. As used herein, "single coating" refers to a single coating without any additional coating. Therefore, the coating composition can be applied directly to the substrate and cured to form a single coating, i.e., a single layer.

[0238] The coated substrate of this disclosure may further comprise one or more additional coatings, such as a second outer coating deposited onto at least a portion of the first coating composition, to form a multilayer coating, as by applying a topcoat. When forming a multilayer coating, the first coating composition may be cured before applying the additional outer coatings, or one or more of the additional outer coatings and the first coating composition may be cured simultaneously. It should be understood that the second outer coating and the additional outer coatings may be in solid or liquid form. The coating composition may be layered under a topcoat or a series of topcoats to form a stack. The coating composition may be a first layer applied as a base coat or primer to a bare substrate. The primer may then have subsequent layers applied on top of it to form a multilayer coating.

[0239] The packaging coating compositions of the present invention can be applied to a variety of substrates. Therefore, this disclosure further relates to a substrate which is at least partially coated with a coating deposited by the packaging coating compositions described herein. For example, the compositions of this disclosure are suitable for use as packaging coatings. Various pretreatments and coatings for packaging are well-established. For example, such treatment materials and / or coatings can be used in the case of metal cans, wherein the treatment materials and / or coatings are used to delay or inhibit corrosion, provide a decorative coating, facilitate handling during manufacturing, etc. Coatings can be applied to the interior of such cans to prevent the contents from coming into contact with the metal of the container. Contact between metal and food or beverage can, for example, lead to corrosion of the metal container, which can potentially contaminate the food or beverage. This is especially true when the contents of the can are inherently acidic. Coatings applied to the interior of metal cans also help prevent corrosion of the can top space in the area between the product fill line and the can lid; corrosion of the top space is particularly problematic for food products with high salt content. Coatings can also be applied to the exterior of metal cans. Certain coatings of this invention are particularly suitable for coiled metal blanks, such as coiled metal blanks for manufacturing can ends (“can end blanks”) and coiled metal blanks for manufacturing end caps and seals (“cap / seal blanks”). Because coatings designed for can end blanks and cap / seal blanks are typically applied before the workpiece is cut and stamped out of the coiled metal blank, the coatings are generally flexible and stretchable. For example, such blanks are typically coated on both sides. The coated metal blank is then stamped. For can ends, “easy-open” openings are then etched into the metal, and easy-open rings are attached with separately manufactured bolts. The ends are then attached to the can body via a roll-flanging process. A similar procedure is performed for “easy-open” can ends. For easy-open can ends, notches essentially around the perimeter of the cap allow the cap to be easily opened or removed from the can, typically by a pull tab. For caps and seals, the caps / seals are typically coated, such as by roll coating, and the caps or seals are stamped from the blank; however, the caps / seals can be coated post-formed. Under relatively stringent temperature and / or pressure requirements, the coating used for cans should also be able to prevent cracking, corrosion, whitening, and / or blistering.

[0240] Therefore, the present invention further relates to packaging at least partially coated with any of the above-described coating compositions. "Packaging" is any substance intended to contain another article, particularly for transport from the point of manufacture to the consumer, and subsequently stored by the consumer. Thus, packaging will be understood as a substance sealed to prevent its contents from spoiling before being opened by the consumer. Manufacturers typically determine the length of time during which food or beverages will not spoil, usually ranging from several months to several years. Therefore, the "packaging" of the present invention differs from storage containers or baking pans that consumers can make and / or store food in; such containers only maintain the freshness or integrity of food articles for a relatively short period. Packaging according to the invention can be made of metal or non-metal, such as plastic or laminate, and can be in any form. Suitable packaging is laminated tubing. Another suitable packaging is a metal can. The term "metal can" includes any type of metal can, container, or part of any type of container sealed by a food / beverage manufacturer to minimize or eliminate spoilage of the contents until the consumer opens such packaging. One type of metal can is a food can; the term "food can" is used herein to refer to a can, container, or reservoir of any type or part thereof used to contain any type of food and / or beverage. "Beverage can" can also be used more specifically to refer to a food can in which a beverage is packaged. The term "metal can" specifically includes food cans (including beverage cans) and also specifically includes "can ends," which include "EZ open ends," typically stamped from can end material and used in conjunction with food and beverage packaging. The term "metal can" also specifically includes metal caps and / or closures, such as bottle caps, screw-top caps, and lids of any size, snap-on caps, etc. Metal cans can also be used to contain other items, including but not limited to personal care products, insect sprays, paints, and any other compounds suitable for packaging in aerosol cans. Cans can include "two-piece cans" and "three-piece cans," as well as thin-walled stretched integral cans; such integral cans are frequently used for aerosol products. Packaging coated according to the invention can also include plastic bottles, plastic tubes, laminates, and flexible packaging, such as those made of PE, PP, PET, etc. This type of packaging can hold items such as food, toothpaste, and personal care products.

[0241] The coating can be applied to the interior and / or exterior of the packaging. For example, the coating can be roll-coated onto the metal used to manufacture three-piece metal cans, can end blanks, and / or cap / seal blanks, or sprayed, flow-coated, gravure-coated, or roll-coated onto the formed two-piece metal cans. The coating is applied to rolls or sheets by roll coating; then the coating is cured by radiation, and the can end is stamped to form the finished product, i.e., the can end. The coating can also be applied as a side coating to the bottom of the can; such application can be done by roll coating. Side coatings are used to reduce friction during the ongoing manufacture and / or processing of the can to improve handling and protection. The coating can also be applied to the cap and / or seal; such application can include, for example, a protective varnish applied before and / or after cap / seal formation and / or colored enamel pillars applied to the cap, particularly those with scoreed seams at the bottom of the cap. Decorative can blanks can also be partially coated externally with the coatings described herein, and decorative, coated can blanks are used to form various metal cans.

[0242] It should be understood that the coating composition of the present invention is suitably formulated for application to can ends above the scribe lines. Formation of the can end may include applying the coating composition to a metal coil and curing the coating composition to form a cured film. The coated coil is then subjected to pressing, bending, and stamping to transform the coil into a can end. The coating should be able to withstand these mechanical requirements. For example, the coating composition may have sufficient flexibility, adhesion to the substrate, hardness, and / or lubricity.

[0243] A can may include a can body and can ends. Suitable cans include, but are not limited to, one or more of the following: two-piece cans, three-piece cans, etc. The can may be a beverage can.

[0244] The can can be formed from any suitable material. Suitablely, the can can be formed from metal. Suitable metals are well known to those skilled in the art. Suitable metals include, but are not limited to, the following: steel; tinplate; tinplate pretreated with a protective material such as chromium, titanium, titanate, or aluminum; tin-free steel (TFS); galvanized steel, such as, for example, electro-galvanized steel; aluminum; aluminum alloys; and combinations thereof. Those skilled in the art will understand that the body and end of a beverage can can be formed from the same or different materials, such as the same or different metals. Suitablely, the body and end of a beverage can can be formed from the same material, such as the same metal.

[0245] The can body and / or can end can be made from rolled sheet metal. Suitably, at least the can end can be made from rolled sheet metal. Suitably, the coating composition of the present invention can be applied to sheet metal, such as sheet metal for manufacturing can ends (“can end stock”).

[0246] The coating composition can be applied to the can end material before the can end is cut and stamped from the metal coil. The can end can be coated on one or both surfaces. Thus, the can coil material can be coated on one or both surfaces before the can end is cut and stamped from the metal coil.

[0247] Advantageously, coating both surfaces of the metal coil provides sufficient lubrication to allow the coating to withstand stamping operations.

[0248] A can end with a cross line can be called an "easy-open" can end, sometimes referred to as an "easy-open end" or even an "EOE".

[0249] Appropriately, after the can end is stamped from a roll of sheet metal, a scribing line is applied to the can end.

[0250] Once the can end is manufactured, it is suitably attached to the can body. The can end can be attached to the can body by any suitable method. Suitably, the can end can be attached to the can body by edge rolling.

[0251] The coating composition may be applied to at least a portion of the scribed lines on the inner surface of the can end, or it may be applied to all of the scribed lines.

[0252] The coating composition may be applied to substantially all or a portion of the inner surface of the can end, provided that the coating composition is applied to at least a portion of the inner surface of the can end above at least a portion of the scribe lines. Suitably, the coating composition may be applied to substantially all of the inner surface of the can end. The coating composition may be applied to at least a portion of the outer surface of the can end. The coating composition may be applied to substantially all or a portion of the outer surface of the can end. Suitably, the coating composition may be applied to the outer surface of the can end above at least a portion of the scribe lines. The coating composition may be applied to at least a portion of the inner and / or outer surfaces of the can body.

[0253] The coating composition can be applied to beverage cans by any suitable method. Methods for applying the coating composition are well known to those skilled in the art. Suitable application methods include, but are not limited to, one or more of the following: spraying, roller coating, dip coating, and / or electrocoating.

[0254] The coating composition can be applied to any suitable dry film thickness. The coating composition can be applied to dry film thicknesses of 0.1 μm to 12 μm, suitably 2 μm to 8 μm, more suitably 4 μm to 7 μm, or even 4 μm to 6 μm.

[0255] The packaging-coated articles envisioned in this disclosure can exhibit high adhesion. For example, after an acetic acid test according to ASTM D3359-22, the coated articles can have an adhesion of 0B or higher, 1B or higher, 2B or higher, 3B or higher, 4B or higher, or 5B.

[0256] This disclosure also envisions a method for forming an article coated with a packaging coating composition. The coating composition may be applied as a single layer or as part of a multilayer system to a substrate or a portion thereof. Suitable substrates include aluminum, tinplate, stainless steel, food packaging, beverage packaging, or metal cans.

[0257] The coating composition can be applied as a single layer. The coating composition can be applied to an uncoated substrate. For the avoidance of doubt, the uncoated substrate extends to a clean surface prior to application. The coating composition can be applied as part of a multilayer system over another paint layer. For example, the coating composition can be applied over a primer. The coating composition can form an intermediate layer or a topcoat. The coating composition can be applied as the first coating layer in a multilayer system. The coating composition can be applied as a base coat or primer. The second, third, fourth, etc., coatings can contain any suitable paint, such as paints containing, for example, epoxy resins; polyester resins; polyurethane resins; polysiloxane resins; hydrocarbon resins or combinations thereof. The second, third, fourth, etc., coatings can include polyester resins. The second, third, fourth, etc., coatings can be liquid coatings or powder coatings.

[0258] Those skilled in the art will understand that coating compositions can be applied before or after the formation of articles such as packaging. For example, a coating composition can be applied to a metal substrate, which is then molded to form a metal article, or the coating composition can be applied to a pre-formed article. The coating composition can be applied to the substrate once or multiple times.

[0259] The coating composition can be applied to a substrate by any suitable method. Methods for applying the coating composition are well known to those skilled in the art. Suitable methods for applying the coating composition include, but are not limited to, electroplating; spraying; electrostatic spraying; dip coating; roller coating; brush coating; etc.

[0260] Example

[0261] I. Synthesis Examples

[0262] A. Synthesis of isocyanate prepolymers

[0263] The isocyanate-terminated prepolymer is prepared by reacting an excess of polyisocyanate with a polyol or alcohol at 60°C–90°C in the presence of a polyurethane catalyst (such as dibutyltin dilaurate (DBTDL)).

[0264] Add isophorone diisocyanate (IPDI, commercially available from Covestro LLC) and DBTDL to a suitable four-necked flask equipped with an electrically driven stainless steel stirrer, a water-cooled condenser, a nitrogen layer, and a heating mantle with a thermometer connected via a temperature feedback control device. Heat the reaction mixture to 60°C–80°C. Then, add the polyol or alcohol to the reaction mixture over 1 hour. After addition, maintain the reaction mixture at 60°C–80°C until the measured isocyanate equivalent weight (NCO EQ Wt) stops changing.

[0265] Titration was performed using a Metrohm 888 Titrando. The titrant consisted of 20 mL of dibutylamine and 980 mL of tetrahydrofuran, along with a solution of 0.2 N HCl in 0.2 N isopropanol.

[0266] Table 5

[0267] Synthesis of isocyanate prepolymers

[0268]

[0269] The prepolymers provided in the table above were formed and characterized. Their structures are shown below.

[0270] Table 6

[0271] Structure of prepolymer

[0272]

[0273] B. Synthesis of Oxazolidinone

[0274] The oxazolidinone-modified resin was prepared according to the following procedure: Charge 1 was added to a suitable four-necked flask equipped with an electrically driven stainless steel stirring blade, a water-cooled condenser, a nitrogen layer, and a heating mantle with a thermometer connected via a temperature feedback control device. The reaction mixture was heated to 170°C to 175°C. Then, charge 2 was added dropwise to the reaction mixture over 1 hour. After addition, the reaction mixture was maintained at 170°C to 180°C until an IR spectrum performed using a ThermoScientific Nicolet iS5 FT-IR spectrometer showed no NCO characteristic band (2269 cm⁻¹). -1 Then, the reaction mixture is cooled to 120°C and poured from the flask into a metal can to form a powdered resin.

[0275] Table 7

[0276] Synthesis of oxazolidinone

[0277]

[0278] Eponex 1510, Epon 828 and TSR-400 are commercially available from Hexion Specialty Chemicals, and tetrabutylphosphonium bromide is commercially available from Sigma Aldrich.

[0279] The structures of the compounds synthesized through the above examples are provided in the table below.

[0280] Table 8

[0281] Structure of compounds

[0282]

[0283] C. Synthesis of OH-functional oxazolidinones

[0284] Add charges 1 and 2 to a suitable four-necked flask equipped with an electrically driven stainless steel stirrer, a water-cooled condenser, a nitrogen layer, and a heating mantle with a thermometer connected via a temperature feedback control device. Heat the reaction mixture to 120°C. Maintain the reaction mixture until AV is less than 2. Then, distill the solvent under vacuum to form a powdered resin or cool the reaction mixture to 40°C and pour it off.

[0285] Table 9

[0286] Synthesis of hydroxyfunctional oxazolidinones

[0287]

[0288] The structures of the compounds synthesized through the above examples are provided in the table below.

[0289] Table 10

[0290] Structure of compounds

[0291]

[0292] D. Synthesis of hydroxyfunctional oxazolidinones for liquid application

[0293] Add charge 1 to a suitable four-necked flask equipped with an electrically driven stainless steel stirrer, a water-cooled condenser, a nitrogen layer, and a heating mantle with a thermometer connected via a temperature feedback control device. Heat the reaction mixture to 170°C to 175°C. Then, add charge 2 dropwise to the reaction mixture over 1 hour. After addition, maintain the reaction mixture at 170°C to 180°C until an IR spectrum performed using a Thermo Scientific Nicolet iS5 FT-IR spectrometer shows no NCO characteristic band (2269 cm⁻¹). -1 The reaction mixture is then cooled to 120°C, and charge 3 is added to the reaction mixture and held until AV is less than 2. The reaction mixture is then cooled to 40°C and poured out.

[0294] Table 11

[0295] Synthesis of hydroxyfunctional oxazolidinones

[0296]

[0297] The structures of the compounds synthesized through the above examples are provided in the table below.

[0298] Table 12

[0299] Structure of compounds

[0300]

[0301] E. Synthesis of hydroxyfunctional oxazolidinones for powder coating

[0302] Add charge 1 to a suitable four-necked flask equipped with an electrically driven stainless steel stirrer, a water-cooled condenser, a nitrogen layer, and a heating mantle with a thermometer connected via a temperature feedback control device. Heat the reaction mixture to 170°C to 175°C. Then add charge 2 dropwise to the reaction mixture over 1 hour. After addition, maintain the reaction mixture at 170°C to 180°C until an IR spectrum performed using a Thermo Scientific Nicolet iS5 FT-IR spectrometer shows no NCO characteristic band (2269 cm⁻¹). -1 The reaction mixture was then cooled to 120°C, and charge 3 was added to the reaction mixture and held until AV was less than 2. The reaction mixture was then distilled under vacuum to remove the solvent and poured off to form a powdered resin.

[0303] Table 13

[0304] Synthesis of hydroxyfunctional oxazolidinones

[0305]

[0306] The structures of the compounds synthesized through the above examples are provided in the table below.

[0307] Table 14

[0308] Structure of compounds

[0309]

[0310] F. Synthesis of carboxylic acid-functionalized oxazolidinones for powder coating

[0311] The acid-functional oxazolidinone resin was formed according to the following procedure: Charge 1 was added to a suitable four-necked flask equipped with an electrically driven stainless steel stirrer, a water-cooled condenser, a nitrogen layer, and a heating mantle with a thermometer connected via a temperature feedback control device. The reaction mixture was heated to 170°C to 175°C. Charge 2 was then added dropwise to the reaction mixture over 1 hour. After addition, the reaction mixture was maintained at 170°C to 180°C until an IR spectrum performed using a Thermo Scientific Nicolet iS5 FT-IR spectrometer showed no NCO characteristic band (2269 cm⁻¹). -1 Then, cool the reaction mixture to 100°C. Add charge 3 to the reaction mixture and maintain at 150°C until an AV of less than 2 is obtained using a 0.1 N KOH solution in methanol as a reagent (3 to 4 hours). Then add charge #4 to the reaction mixture. Heat the reaction mixture to 150°C and maintain until an IR spectrum performed using a ThermoScientific Nicolet iS5 FT-IR instrument shows no characteristic bands of ε-caprolactone (850 and 860 cm⁻¹). Then add charge 5 to the reaction mixture. Maintain the reaction mixture at 150°C until an IR spectrum shows no characteristic bands of anhydride (1768 cm⁻¹). -1 The reaction mixture was distilled under vacuum to remove the solvent and poured off to form a powdered resin.

[0312] Table 15

[0313] Synthesis of acid-functional oxazolidinones

[0314]

[0315] The structures of the compounds synthesized through the above examples are provided in the table below.

[0316] Table 16

[0317] Structure of compounds

[0318]

[0319] G. Synthesis of carboxylic acid-functionalized oxazolidinones for liquid coatings

[0320] The acid-functional oxazolidinone resin was formed according to the following procedure: Charge #1 was added to a suitable four-necked flask equipped with an electrically driven stainless steel stirrer, a water-cooled condenser, a nitrogen layer, and a heating mantle with a thermometer connected via a temperature feedback control device. The reaction mixture was heated to 170°C to 175°C. Charge #2 was then added dropwise to the reaction mixture over 1 hour. After addition, the reaction mixture was maintained at 170°C to 180°C until an IR spectrum performed using a Thermo Scientific Nicolet iS5 FT-IR spectrometer showed no NCO characteristic band (2269 cm⁻¹). -1 Then, cool the reaction mixture to 100°C. Add charge 3 to the reaction mixture and maintain at 150°C until an AV of less than 2 is obtained using a 0.1 N KOH solution in methanol as a reagent (3 to 4 hours). Then add charge #4 to the reaction mixture. Heat the reaction mixture to 150°C and maintain until an IR spectrum performed using a ThermoScientific Nicolet iS5 FT-IR instrument shows no characteristic bands of ε-caprolactone (850 and 860 cm⁻¹). Then add charge 5 to the reaction mixture. Maintain the reaction mixture at 150°C until an IR spectrum shows no characteristic bands of anhydride (1768 cm⁻¹). -1 Cool the reaction mixture and pour it out.

[0321] Table 17

[0322] Synthesis of carboxylic acid functional oxazolidinones

[0323]

[0324] The structures of the compounds synthesized through the above examples are provided in the table below.

[0325] Table 18

[0326] Structure of compounds

[0327]

[0328] H. Synthesis of oxazolidinone-functionalized acrylic acids for powder coating

[0329] i. Carboxylic acid oxazolidinone functionalized acrylic acid:

[0330] The oxazolidinone resin was formed according to the following procedure: Charge #1 was added to a suitable 4-necked flask equipped with an electrically driven stainless steel stirrer, a water-cooled condenser, a nitrogen layer, and a heating mantle with a thermometer connected via a temperature feedback control device. The reaction mixture was then heated to reflux (120°C) with stirring. Charge 2 was mixed and added to the reactor over 210 minutes. 15 minutes after charge 2, charge 3 was added to the reactor over 180 minutes. When charge 3 was completely added, feed 4 was used to rinse it. When charge 2 was completely added, feed 5 was used to rinse it. After adding charges 4 and 5, stirring was continued under reflux for 90 minutes. After holding, vacuum distillation was set to remove the solvent. Oxazolidinone-functionalized acrylic powder resin was obtained, and Mw was 31,000.

[0331] Table 19

[0332] Synthesis of carboxylic acid oxazolidinone functionalized acrylic acid for powder

[0333]

[0334] The structures of the compounds synthesized in the above examples are provided in the table below.

[0335] Table 20

[0336] Structure of compounds

[0337]

[0338] ii. Oxazolidinones with mono-IPDI caps:

[0339] The single-IPDI capped resin was prepared according to the following procedure. Charge 1 was added to a suitable four-necked flask equipped with an electrically driven stainless steel stirrer, a water-cooled condenser, a nitrogen layer, and a heating mantle with a thermometer connected via a temperature feedback control device. The reaction mixture was heated to 175°C–180°C. Then, charge 2 was added dropwise to the reaction mixture over 1 hour. After addition, the reaction mixture was maintained at 180°C–185°C until an IR spectrum performed using a Thermo Scientific Nicolet iS5 FT-IR spectrometer showed no NCO characteristic band (2269 cm⁻¹). -1Aliquots were taken to measure the epoxy equivalent weight (EEW) to calculate the required amount of charge 3. The reaction mixture was then cooled to 120°C and charge 3 was added. As the temperature decreased, charge 4 was added. The reaction mixture was maintained at 130°C until the acid value (AV) reached less than 5. To synthesize the mono-IPDI-capped oxazolidinone resin, the reaction mixture was further cooled to 80°C and charge 5 was added. At 80°C, charge 6 was added dropwise to the reaction mixture over 2 hours. After addition, the reaction mixture was maintained at 80°C until an IR spectrum performed using a Thermo Scientific Nicolet iS5 FT-IR showed no NCO characteristic band (2269 cm⁻¹). -1 At 80°C, the resin is poured from a flask into a metal container to form a single-IPDI capped powder resin. The molecular weight of the resin, as determined by GPC, is 32363.

[0340] Table 20A

[0341] Synthesis of mono-IPDI-capped oxazolidinones

[0342]

[0343] The structures of compounds from Example S19 are provided below.

[0344]

[0345] II. Examples of E-coating compositions

[0346] A. Oxazolidinone in cationic acrylic E-coating systems

[0347] Synthesis of amination-modified oxazolidinone epoxy resin (additive 1):

[0348] The additive containing cationic oxazolidinone was prepared from the materials included in Table 21 as follows: Materials 1-2 were loaded into a reaction vessel and heated to 60°C under a nitrogen atmosphere. Material 3 was added and the reaction was allowed to proceed exothermally to approximately 100°C. Once the reaction reached 100°C, it was maintained for one hour. The epoxy equivalent weight was then checked and found to be infinite after one hour (all epoxy resin had been consumed). Material 4 was then added to the mixture under gentle stirring, followed by material 5. The mixture was then stirred for one hour and then poured off.

[0349] Table 21

[0350] Components in Additive 1:

[0351]

[0352] Formulation results:

[0353] The corrosion performance was then evaluated by adding a water-dispersed, amination-modified oxazolidinone epoxy resin (Additive 1) at 15% of the total bath solids to the commercial PPG cationic acrylic E-coating system Powercron 935 (P935), electrodeposited on bare cold-rolled steel, and repeatedly evaluating its corrosion performance in neutral salt spray (ASTM B117-19) by measuring scribing creep three times after 1000 hours (Table 22). While a 1% additive load provided poorer scribing creep (23.5 mm vs. 19.9 mm, respectively) compared to 0%, additive loads of 4.5% (10.2 mm) and 10% (9.3 mm) both provided improved results compared to the control (0% load).

[0354] Table 22

[0355] Preparation and corrosion results:

[0356]

[0357] B. Oxazolidinone in cationic epoxy E-coating systems

[0358] Synthesis of blocked polyisocyanate curing agents (crosslinking agents)

[0359] The blocked polyisocyanate curing agent was prepared as follows: Components 2-5 listed in Table 23 were mixed in a flask set to complete reflux under nitrogen atmosphere and with stirring. The mixture was heated to 30°C, and component 1 was added dropwise, causing the temperature to rise due to the exothermic reaction and maintained at 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 was maintained at the temperature until no residual isocyanate was detected by IR spectroscopy. Component 6 was then added, and the reaction mixture was stirred at 100°C for 30 minutes before being poured off, allowing it to cool to ambient temperature.

[0360] Table 23

[0361] Synthesis of blocked polyisocyanate curing agents (crosslinking agents):

[0362]

[0363] C. Synthesis of oxazolidinone-containing cationic epoxy E-coating polymers

[0364] Mix components 1 through 6 listed in Table 8 in a flask set for total reflux while stirring under nitrogen. Heat the mixture to 130°C and allow exothermic reaction (up to 175°C). Establish a temperature of 145°C in the reaction mixture and maintain the reaction mixture for 2 hours. Slowly introduce component 7 while cooling the mixture to 125°C, followed by the addition of component 8. Establish a temperature of 105°C and then rapidly add (sequentially) components 10 and 11 to the reaction mixture, allowing the reaction mixture to exothermic reaction. Establish a temperature of 120°C and maintain the reaction mixture for 1 hour. Then, pour the product into a premixed solution of components 12-13 to form a resin dispersion and stir the resin dispersion for 1 hour. Then, introduce component 14 over 30 minutes to further dilute the resin dispersion, followed by the addition of component 15. Remove free MIBK from the resin dispersion under vacuum at a temperature of 60°C–70°C.

[0365] Table 24

[0366] Synthesis of cationic epoxy E-coating polymers containing oxazolidinone

[0367]

[0368] Formulation results:

[0369] The polymers in Table 23 were evaluated as 'clear' formulations (no pigment) with a total bath solids of 33%. Two commercial PPG systems were also evaluated as controls (Powercron 10X and Fram E-coat II). All systems were electrodeposited on cold-rolled steel pretreated with C700 (zinc phosphate) and their corrosion performance in neutral salt spray (ASTM B117-19) was evaluated twice after 1000 hours by measuring scribing creep (Table 24). Incorporation of oxazolidinone into the primary electrocoating polymer provided improved scribing corrosion results compared to commercial systems without the oxazolidinone component.

[0370] Table 25

[0371] Preparation and corrosion results:

[0372]

[0373] III. Examples of Powder Coating Compositions

[0374] A. Preparation of coating compositions by reacting oxazolidinones with one or two terminal epoxy groups with monoisocyanates.

[0375] Each of the components listed in the table below was weighed in a container and mixed at 3500 RPM for 30 seconds in a prismatic high-speed mixer to form a dry, homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19 mm twin-screw extruder in an active screw configuration at 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 resulted in 45%–55% torque being observed on the equipment. After exiting the extruder, the mixture was dripped onto a set of cooling rollers to cool and re-solidify into solid fragments. The fragments were weighed and 0.15 wt.% Aerosil 200 was added based on the total weight of the composition. The mixture was then milled in a Mikro ACM®-1 air classifier mill to obtain a particle size of 5 to 90 micrometers, with most particles being 20 to 50 micrometers and an average particle size of approximately 27 to 32 micrometers, as determined by dynamic light scattering as measured by Mie scattering and Fraunhofer diffraction techniques according to ISO 13320-1 practice. The resulting coating composition for each example is a free-flowing solid particle powder coating composition.

[0376] Table 26

[0377] Preparation of powder coatings (in grams)

[0378]

[0379] Application

[0380] The powder coating compositions prepared above were applied using an Encore Nordson powder coating cup gun under 75 kV, 15 mA limitation, 10 psi atomization, and 10 psi delivery airflow. The coating thickness of the single-coat compositions ranged from 64 µm to 83 µm. The coatings were cured at 375℉ for 20 minutes to form a single coating. The substrates on which the coatings were tested are listed below.

[0381] test

[0382] Comparative corrosion examples were tested by exposing metal to the ASTM B117 salt spray corrosion test panel and the SAE J2334 cyclic corrosion test panel, with scribing cuts made to the center of the panel. The metal was exposed on both a 4-inch × 6-inch B117 corrosion test panel and a 4-inch × 8-inch cyclic corrosion test panel. The panel substrate and pretreatment type are listed along with the corrosion results. After testing, loose coatings and corrosion products on the panels were scraped off under a stream of warm water. The scribing creep of the exposed metal and corrosion products was measured as the total scribing creep across the exposed area at a 90° angle to the scribing line. An average of 10 readings on both panels is reported in millimeters. The average total scribing creep for cyclic corrosion is reported in the table below, with 5 readings per panel for the B117 panel.

[0383] Table 27

[0384] 500-hour B117 corrosion test

[0385]

[0386] Table 28

[0387] 768-hour B117 corrosion test

[0388]

[0389] Table 29

[0390] 768-hour B117 corrosion test

[0391]

[0392] Table 30

[0393] 40 cycles of SAE J2334 cyclic corrosion test

[0394]

[0395] Table 31

[0396] Additional testing of B1000 P99X ACT substrate

[0397]

[0398] The results showed that, compared with PC1, the B117 salt spray etching corrosion and SAE J2334 corrosion in Examples PC2 and PC3 were improved, with one epoxy functional group being "capped" by an oxazolidinone group, and two epoxy functional groups being "capped" by oxazolidinone groups. Oxazolidinone additives are inherently "non-functional" and do not participate in crosslinking or participate in crosslinking with limited (monofunctional) capacity. When non-functional, oligomers containing oxazolidinone and having terminal oxazolidinone groups are now essentially corrosion inhibitors.

[0399] B. Preparation of coating compositions using monoisocyanates with capped oxazolidinone epoxy groups

[0400] Each of the components listed in the table below was weighed in a container and mixed at 3500 RPM for 30 seconds in a prismatic high-speed mixer to form a dry, homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19 mm twin-screw extruder in an active screw configuration at 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 resulted in 45%–55% torque being observed on the equipment. After exiting the extruder, the mixture was dripped onto a set of cooling rollers to cool and re-solidify into solid fragments. The fragments were weighed and 0.15 wt.% Aerosil 200 was added, followed by milling in a Mikro ACM®-1 air classifier mill to obtain a particle size of 5 to 90 micrometers, with most particles being 20 to 50 micrometers and an average particle size of approximately 27–32 micrometers. The resulting coating composition for each example is a free-flowing solid particulate powder coating composition.

[0401] Table 32

[0402] Preparation of powder coatings (in grams)

[0403]

[0404] Application

[0405] The cured powder coating compositions prepared above were applied using an Encore Nordson powder coating cup gun under 75 kV, 15 mA limitation, 10 psi atomization, and 10 psi delivery airflow. The coating thickness of the single-coat compositions ranged from 64 µm to 83 µm. The coatings were cured at 375℉ for 20 minutes to form a single coating. The substrates on which the coatings were tested are listed below.

[0406] test

[0407] According to ASTM B117 salt spray corrosion, a comparative corrosion example was tested by scribing to the center of the panel, exposing the metal on a 4-inch × 6-inch B117 corrosion test panel. The panel substrate and pretreatment type are listed along with the corrosion results. After testing, loose coatings and corrosion products on the panel were scraped off under a stream of warm water. The scribing creep of the exposed metal and corrosion products was measured as the total scribing creep through the exposed area at a 90° angle to the scribing. The average of five readings on both panels is reported in millimeters, and the average total scribing creep is reported in the table below.

[0408] Table 33

[0409] 500-hour B117 corrosion test

[0410]

[0411] Table 34

[0412] 744-hour B117 corrosion test

[0413]

[0414] Table 35

[0415] 1200-hour B117 corrosion test

[0416]

[0417] Table 36

[0418] Additional testing of B1000 P99X ACT substrate

[0419]

[0420] The results showed that, compared with control PC4, the B117 salt spray scratch corrosion in examples PC5, PC6, PC7, PC8, PC9, and PC10 was improved. One epoxy functional group was "capped" by an oxazolidinone group, and two epoxy functional groups were "capped" by oxazolidinone groups formed from the reaction of terminal epoxides with monoisocyanates. This indicates that corrosion resistance can be enhanced even at loadings as low as 1%, provided that epoxy functional groups are essentially not incorporated into the polymer crosslinking network. Oxazolidinone-containing oligomers with terminal oxazolidinone groups can essentially act as corrosion inhibitors.

[0421] C. Preparation of coating compositions using IPDI-based oxazolidinones reacted with end-group epoxy resins and monoisocyanates.

[0422] Each of the components listed in the table below was weighed in a container and mixed at 3500 RPM for 30 seconds in a prismatic high-speed mixer to form a dry, homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19 mm twin-screw extruder in an active screw configuration at 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 resulted in 45%–55% torque being observed on the equipment. After exiting the extruder, the mixture was dripped onto a set of cooling rollers to cool and re-solidify into solid fragments. The fragments were weighed and 0.15 wt.% Aerosil 200 was added, followed by milling in a Mikro ACM®-1 air classifier mill to obtain a particle size of 5 to 90 micrometers, with most particles being 20 to 50 micrometers and an average particle size of approximately 27–32 micrometers. The resulting coating composition for each example is a free-flowing solid particulate powder coating composition.

[0423] Table 37

[0424] Preparation of powder coatings (in grams)

[0425]

[0426] Application

[0427] The cured powder coating compositions prepared above were applied using an Encore Nordson powder coating cup gun under 75 kV, 15 mA limitation, 10 psi atomization, and 10 psi delivery airflow. The coating thickness of the single-coat compositions ranged from 64 µm to 83 µm. The coatings were cured at 375℉ for 20 minutes to form a single coating. The substrates on which the coatings were tested are listed below.

[0428] test

[0429] According to ASTM B117 salt spray corrosion, a comparative corrosion example was tested by scribing to the center of the panel, exposing the metal on a 4-inch × 6-inch B117 corrosion test panel. The panel substrate and pretreatment type are listed along with the corrosion results. After testing, loose coatings and corrosion products on the panel were scraped off under a stream of warm water. The scribing creep of the exposed metal and corrosion products was measured as the total scribing creep through the exposed area at a 90° angle to the scribing. The average of five readings on both panels is reported in millimeters, and the average total scribing creep is reported in the table below.

[0430] Table 38

[0431] 500-hour B117 corrosion test

[0432]

[0433] Table 39

[0434] 768-hour B117 corrosion test

[0435]

[0436] Table 40

[0437] Additional testing of B1000 P99X ACT substrate

[0438]

[0439] Compared to example PC11, the B117 salt spray etching corrosion in examples PC12, PC13, PC14, and PC15 was improved. In these examples, one epoxy functional group was "capped" by reacting with a monoisocyanate; in the second example, both epoxy functional groups were "capped" by a monoisocyanate. This more aliphatic oxazolidinone demonstrates that corrosion resistance can be enhanced by restricting the structure to essentially the absence of epoxy functional groups within a more aliphatic framework.

[0440] D. Preparation of coating compositions using oxazolidinone dieoxy resins in which epoxy groups are removed by reaction with a monobasic acid.

[0441] Each of the components listed in the table below was weighed in a container and mixed at 3500 RPM for 30 seconds in a prismatic high-speed mixer to form a dry, homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19 mm twin-screw extruder in an active screw configuration at 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 resulted in 45%–55% torque being observed on the equipment. After exiting the extruder, the mixture was dripped onto a set of cooling rollers to cool and re-solidify into solid fragments. The fragments were weighed and 0.15 wt.% Aerosil 200 was added, followed by milling in a Mikro ACM®-1 air classifier mill to obtain a particle size of 5 to 90 micrometers, with most particles being 20 to 50 micrometers and an average particle size of approximately 27–32 micrometers. The resulting coating composition for each example is a free-flowing solid particulate powder coating composition.

[0442] Table 41

[0443] Preparation of powder coatings (in grams)

[0444]

[0445] Application

[0446] The cured powder coating compositions prepared above were applied using an Encore Nordson powder coating cup gun under 75 kV, 15 mA limitation, 10 psi atomization, and 10 psi delivery airflow. The coating thickness of the single-coat compositions ranged from 64 µm to 83 µm. The coatings were cured at 375℉ for 20 minutes to form a single coating. The substrates on which the coatings were tested are listed below.

[0447] test

[0448] According to ASTM B117 salt spray corrosion, a comparative corrosion example was tested by scribing to the center of the panel, exposing the metal on a 4-inch × 6-inch B117 corrosion test panel. The panel substrate and pretreatment type are listed along with the corrosion results. After testing, loose coatings and corrosion products on the panel were scraped off under a stream of warm water. The scribing creep of the exposed metal and corrosion products was measured as the total scribing creep through the exposed area at a 90° angle to the scribing. The average of five readings on both panels is reported in millimeters, and the average total scribing creep is reported in the table below.

[0449] Table 42

[0450] 500-hour B117 corrosion test

[0451]

[0452] Table 43

[0453] 500-hour B117 corrosion test

[0454]

[0455] Table 44

[0456] 768-hour B117 corrosion test

[0457]

[0458] Table 45

[0459] 1296-hour B117 corrosion test

[0460]

[0461] The results showed that, compared to PC16, the B117 salt spray etching corrosion in Examples PC17 and PC18 was improved, where the epoxy end groups reacted with the monobasic acid, but the diepoxide oxazolidinone had a fully aliphatic structure. Utilizing this structure, performance can be enhanced by restricting the polymer crosslinking network to essentially without incorporating epoxy functional groups. The oligomer containing the oxazolidinone and whose terminal epoxy groups react with the acid is now essentially a corrosion inhibitor that does not crosslink into the polymer network. The secondary hydroxyl groups do not participate in the crosslinking reaction.

[0462] E. Preparation of carbamate crosslinked powder coating compositions using diepoxyoxazolidinones that react their epoxy groups with monobasic acids.

[0463] Each of the components listed in the table below was weighed in a container and mixed at 3500 RPM for 30 seconds in a prismatic high-speed mixer to form a dry, homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19 mm twin-screw extruder in an active screw configuration at 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 resulted in 45%–55% torque being observed on the equipment. After exiting the extruder, the mixture was dripped onto a set of cooling rollers to cool and re-solidify into solid fragments. The fragments were weighed and 0.15 wt.% Aerosil 200 was added, followed by milling in a Mikro ACM®-1 air classifier mill to obtain a particle size of 5 to 90 micrometers, with most particles being 20 to 50 micrometers and an average particle size of approximately 27–32 micrometers. The resulting coating composition for each example is a free-flowing solid particulate powder coating composition.

[0464] Table 46

[0465] Preparation of powder coatings (in grams)

[0466]

[0467] Application

[0468] The cured powder coating compositions prepared above were applied using an Encore Nordson powder coating cup gun under 75 kV, 15 mA limitation, 10 psi atomization, and 10 psi delivery airflow. The coating thickness of the single-coat compositions ranged from 64 µm to 83 µm. The coatings were cured at 375℉ for 20 minutes to form a single coating. The substrates on which the coatings were tested are listed below.

[0469] test

[0470] According to ASTM B117 salt spray corrosion, a comparative corrosion example was tested by scribing to the center of the panel, exposing the metal on a 4-inch × 6-inch B117 corrosion test panel. The panel substrate and pretreatment type are listed along with the corrosion results. After testing, loose coatings and corrosion products on the panel were scraped off under a stream of warm water. The scribing creep of the exposed metal and corrosion products was measured as the total scribing creep through the exposed area at a 90° angle to the scribing. The average of five readings on both panels is reported in millimeters, and the average total scribing creep is reported in the table below.

[0471] Table 47

[0472] 500-hour B117 corrosion test

[0473]

[0474] Table 48

[0475] 500-hour B117 corrosion test

[0476]

[0477] Table 49

[0478] 1296-hour B117 corrosion test

[0479]

[0480] Table 50

[0481] Additional testing of B1000 P99X ACT substrate

[0482]

[0483] The results showed that, in these urethane crosslinked powder coating formulations, the more aliphatic PC21 and PC22 improved B117 salt spray scratch corrosion, but not in the aromatic example PC20. These formulations were modified with a hydroxyl-functionalized oxazolidinone, which is produced by ring-opening a diepoxyoxazolidinone with benzoic acid, leaving a secondary hydroxyl group for crosslinking. Oxazolidinone additives can be crosslinked into systems with hydroxyl functional groups and provide improved corrosion resistance when the structure is inherently more aliphatic.

[0484] F. Preparation of powder coatings with oxazolidinone diepoxide structures that react with monobasic acids to remove epoxy functional groups.

[0485] Each of the components listed in the table below was weighed in a container and mixed at 3500 RPM for 30 seconds in a prismatic high-speed mixer to form a dry, homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19 mm twin-screw extruder in an active screw configuration at 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 resulted in 45%–55% torque being observed on the equipment. After exiting the extruder, the mixture was dripped onto a set of cooling rollers to cool and re-solidify into solid fragments. The fragments were weighed and 0.15 wt.% Aerosil 200 was added, followed by milling in a Mikro ACM®-1 air classifier mill to obtain a particle size of 5 to 90 micrometers, with most particles being 20 to 50 micrometers and an average particle size of approximately 27–32 micrometers. The resulting coating composition for each example is a free-flowing solid particulate powder coating composition.

[0486] Table 51

[0487] Preparation of powder coatings (in grams)

[0488]

[0489] Application

[0490] The cured powder coating compositions prepared above were applied using an Encore Nordson powder coating cup gun under 75 kV, 15 mA limitation, 10 psi atomization, and 10 psi delivery airflow. The coating thickness of the single-coat compositions ranged from 64 µm to 83 µm. The coatings were cured at 375℉ for 20 minutes to form a single coating. The substrates on which the coatings were tested are listed below.

[0491] test

[0492] According to ASTM B117 salt spray corrosion, a comparative corrosion example was tested by scribing to the center of the panel, exposing the metal on a 4-inch × 6-inch B117 corrosion test panel. The panel substrate type is listed along with the corrosion results. After testing, loose coatings and corrosion products on the panel were scraped off under a stream of warm water. The scribing creep of the exposed metal and corrosion products was measured as the total scribing creep through the exposed area at a 90° angle to the scribing. The average of five readings on both panels is reported in millimeters, and the average total scribing creep is reported in the table below.

[0493] Table 52

[0494] 500-hour B117 corrosion test

[0495]

[0496] The results showed that PC24, PC25, and PC26 exhibited improved B117 salt spray scratch corrosion compared to control PC23, which contained all aromatic compounds, IPDI / aromatic compounds, and all aliphatic benzoic acid ring-opening epoxy groups. Oxazolidinones are inherently nonfunctional and were used as additives to improve corrosion resistance in primid-cured polyester single-coat compositions.

[0497] G. Preparation of coating compositions using oxazolidinone acrylate monomers derived from oxazolidinone acrylate monomers.

[0498] Each of the components listed in the table below was weighed in a container and mixed at 3500 RPM for 30 seconds in a prismatic high-speed mixer to form a dry, homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19 mm twin-screw extruder in an active screw configuration at 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 resulted in 45%–55% torque being observed on the equipment. After exiting the extruder, the mixture was dripped onto a set of cooling rollers to cool and re-solidify into solid fragments. The fragments were weighed and 0.15 wt.% Aerosil 200 was added, followed by milling in a Mikro ACM®-1 air classifier mill to obtain a particle size of 5 to 90 micrometers, with most particles being 20 to 50 micrometers and an average particle size of approximately 27–32 micrometers. The resulting coating composition for each example is a free-flowing solid particulate powder coating composition.

[0499] Table 53

[0500] Preparation of powder coatings (in grams)

[0501]

[0502] Application

[0503] The cured powder coating compositions prepared above were applied using an Encore Nordson powder coating cup gun under 75 kV, 15 mA limitation, 10 psi atomization, and 10 psi delivery airflow. The coating thickness of the single-coat compositions ranged from 64 µm to 83 µm. The coatings were cured at 375℉ for 20 minutes to form a single coating. The substrates on which the coatings were tested are listed below.

[0504] test

[0505] According to ASTM B117 salt spray corrosion, a comparative corrosion example was tested by scribing to the center of the panel, exposing the metal on a 4-inch × 6-inch B117 corrosion test panel. The panel substrate and pretreatment type are listed along with the corrosion results. After testing, loose coatings and corrosion products on the panel were scraped off under a stream of warm water. The scribing creep of the exposed metal and corrosion products was measured as the total scribing creep through the exposed area at a 90° angle to the scribing. The average of five readings on both panels is reported in millimeters, and the average total scribing creep is reported in the table below. The test film range for single-coat corrosion testing is 70 to 85 μm.

[0506] Table 54

[0507] 500-hour B117 corrosion test

[0508]

[0509] Table 55

[0510] 744-hour B117 corrosion test

[0511]

[0512] Table 56

[0513] 1296-hour B117 corrosion test

[0514]

[0515] Table 57

[0516] Additional testing of B1000 P99X ACT substrate

[0517]

[0518] The results showed that B117 salt spray corrosion was improved when an acrylic polymer containing oxazolidinone was used as an anti-corrosion additive in the powder coating.

[0519] H. Preparation of oxazolidinone coating compositions based on isocyanate prepolymers with epoxy functional groups using polyTHF 650

[0520] Each of the components listed in the table below was weighed in a container and mixed at 3500 RPM for 30 seconds in a prismatic high-speed mixer to form a dry, homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19 mm twin-screw extruder in an active screw configuration at 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 resulted in 45%–55% torque being observed on the equipment. After exiting the extruder, the mixture was dripped onto a set of cooling rollers to cool and re-solidify into solid fragments. The fragments were weighed and 0.15 wt.% Aerosil 200 was added, followed by milling in a Mikro ACM®-1 air classifier mill to obtain a particle size of 5 to 90 micrometers, with most particles being 20 to 50 micrometers and an average particle size of approximately 27–32 micrometers. The resulting coating composition for each example is a free-flowing solid particulate powder coating composition.

[0521] Table 58

[0522] Preparation of powder coatings (in grams)

[0523]

[0524] Application

[0525] The cured powder coating compositions prepared above were applied using an Encore Nordson powder coating cup gun under 75 kV, 15 mA limitation, 10 psi atomization, and 10 psi delivery airflow. The coating thickness of the single-coat compositions ranged from 64 µm to 83 µm. The coatings were cured at 375℉ for 20 minutes to form a single coating. The substrates on which the coatings were tested are listed below.

[0526] test

[0527] According to ASTM B117 salt spray corrosion, a comparative corrosion example was tested by exposing the metal on a 4-inch × 6-inch B117 corrosion test panel by scribing to the center of the panel. The panel substrate and pretreatment type are listed along with the corrosion results. After testing, loose coatings and corrosion products on the panel were scraped off under a stream of warm water. The scribing creep of the exposed metal and corrosion products was measured as the total scribing creep through the exposed area at a 90° angle to the scribing. The average of five readings from both panels is reported in millimeters of total scribing.

[0528] Table 59

[0529] 500-hour B117 corrosion test

[0530]

[0531] Table 60

[0532] 750-hour B117 corrosion test

[0533]

[0534] Table 61

[0535] 1000-hour B117 corrosion test

[0536]

[0537] Table 62

[0538] Additional testing of B1000 P99X ACT substrate

[0539]

[0540] The results showed that the B117 salt spray scribing corrosion of epoxy-functionalized oxazolidinones based on polyTHF 650 isocyanate prepolymers was improved compared with the unmodified control. This method utilizes epoxy functional groups but has a modified structure based on the polyTHF isocyanate prepolymer structure.

[0541] I. Preparation of epoxy-functionalized oxazolidinone coating compositions using isocyanate prepolymers based on polyTHF 250

[0542] Each of the components listed in the table below was weighed in a container and mixed at 3500 RPM for 30 seconds in a prismatic high-speed mixer to form a dry, homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19 mm twin-screw extruder in an active screw configuration at 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 resulted in 45%–55% torque being observed on the equipment. After exiting the extruder, the mixture was dripped onto a set of cooling rollers to cool and re-solidify into solid fragments. The fragments were weighed and 0.15 wt.% Aerosil 200 was added, followed by milling in a Mikro ACM®-1 air classifier mill to obtain a particle size of 5 to 90 micrometers, with most particles being 20 to 50 micrometers and an average particle size of approximately 27–32 micrometers. The resulting coating composition for each example is a free-flowing solid particulate powder coating composition.

[0543] Table 63

[0544] Preparation of powder coatings (in grams)

[0545]

[0546] Application

[0547] The cured powder coating compositions prepared above were applied using an Encore Nordson powder coating cup gun under 75 kV, 15 mA limitation, 10 psi atomization, and 10 psi delivery airflow. The coating thickness of the single-coat compositions ranged from 64 µm to 83 µm. The coatings were cured at 375℉ for 20 minutes to form a single coating. The substrates on which the coatings were tested are listed below.

[0548] test

[0549] According to ASTM B117 salt spray corrosion, a comparative corrosion example was tested by exposing the metal on a 4-inch × 6-inch B117 corrosion test panel by scribing to the center of the panel. The panel substrate and pretreatment type are listed along with the corrosion results. After testing, loose coatings and corrosion products on the panel were scraped off under a stream of warm water. The scribing creep of the exposed metal and corrosion products was measured as the total scribing creep through the exposed area at a 90° angle to the scribing. The average of five readings from both panels is reported in millimeters of total scribing.

[0550] Table 64

[0551] 500-hour B117 corrosion test

[0552]

[0553] Table 65

[0554] 500-hour B117 corrosion test

[0555]

[0556] Table 66

[0557] Additional testing of B1000 P99X ACT substrate

[0558]

[0559] The results showed that the corrosion resistance of the TGIC and Primid-cured polyester powder compositions was improved when modified with the poly(THF) 250 IPDI prepolymer diepoxide oxazolidinone. We can see that the corrosion resistance of both the longer-chain 650 and shorter-chain 250 versions of poly(THF) was improved.

[0560] J. Preparation of epoxy-functionalized oxazolidinone coating compositions using polyTHF 250-based isocyanates

[0561] Each of the components listed in the table below was weighed in a container and mixed at 3500 RPM for 30 seconds in a prismatic high-speed mixer to form a dry, homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19 mm twin-screw extruder in an active screw configuration at 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 resulted in 45%–55% torque being observed on the equipment. After exiting the extruder, the mixture was dripped onto a set of cooling rollers to cool and re-solidify into solid fragments. The fragments were weighed and 0.15 wt.% Aerosil 200 was added, followed by milling in a Mikro ACM®-1 air classifier mill to obtain a particle size of 5 to 90 micrometers, with most particles being 20 to 50 micrometers and an average particle size of approximately 27–32 micrometers. The resulting coating composition for each example is a free-flowing solid particulate powder coating composition.

[0562] Table 67

[0563] Preparation of powder coatings (in grams)

[0564]

[0565] Application

[0566] The cured powder coating compositions prepared above were applied using an Encore Nordson powder coating cup gun under 75 kV, 15 mA limitation, 10 psi atomization, and 10 psi delivery airflow. The coating thickness of the single-coat compositions ranged from 64 µm to 83 µm. The coatings were cured at 375℉ for 20 minutes to form a single coating. The substrates on which the coatings were tested are listed below.

[0567] test

[0568] According to ASTM B117 salt spray corrosion, a comparative corrosion example was tested by exposing the metal on a 4-inch × 6-inch B117 corrosion test panel by scribing to the center of the panel. The panel substrate and pretreatment type are listed along with the corrosion results. After testing, loose coatings and corrosion products on the panel were scraped off under a stream of warm water. The scribing creep of the exposed metal and corrosion products was measured as the total scribing creep through the exposed area at a 90° angle to the scribing. The average of five readings from both panels is reported in millimeters of total scribing.

[0569] Table 68

[0570] 500-hour B117 corrosion test

[0571]

[0572] Table 69

[0573] 336-hour B117 corrosion test

[0574]

[0575] Table 70

[0576] 1200-hour B117 corrosion test

[0577]

[0578] Table 71

[0579] Additional testing of B1000 P99X ACT substrate

[0580]

[0581] The results showed that the B117 salt spray etching of the polyester powder composition cured by TGIC and Primid was improved when modified with poly(THF 250 IPDI) prepolymer diepoxyoxazolidinone oligomer.

[0582] K. Preparation of coating compositions using acid-functionalized oxazolidinones and polyTHF-based oxazolidinones.

[0583] Each of the components listed in the table below was weighed in a container and mixed at 3500 RPM for 30 seconds in a prismatic high-speed mixer to form a dry, homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19 mm twin-screw extruder in an active screw configuration at 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 resulted in 45%–55% torque being observed on the equipment. After exiting the extruder, the mixture was dripped onto a set of cooling rollers to cool and re-solidify into solid fragments. The fragments were weighed and 0.15 wt.% Aerosil 200 was added, followed by milling in a Mikro ACM®-1 air classifier mill to obtain a particle size of 5 to 90 micrometers, with most particles being 20 to 50 micrometers and an average particle size of approximately 27–32 micrometers. The resulting coating composition for each example is a free-flowing solid particulate powder coating composition.

[0584] Table 72

[0585] Preparation of powder coatings (in grams)

[0586]

[0587] Application

[0588] The prepared cured powder coating composition was applied using an Encore Nordson powder coating cup gun under 75 kV, 15 mA limitation, 10 psi atomization, and 10 psi delivery airflow. The coating thickness of the single-coat composition ranged from 64 µm to 83 µm. The coating was cured in an electric oven at 375℉ for 20 minutes to form a coating layer.

[0589] test

[0590] According to ASTM B117 Salt Spray Corrosion, a comparative corrosion example was tested by scribing to the center of the panel, exposing the metal on a 4-inch × 6-inch test panel. The panel substrate and pretreatment type are listed along with the corrosion results. After testing, loose coatings and corrosion products on the panel were scraped off under a stream of warm water. The scribing creep of the exposed metal and corrosion products was measured as the total scribing creep through the exposed area at a 90° angle to the scribing. The average of five readings from both panels is reported in millimeters, and the total scribing creep is reported in the table below.

[0591] Table 73

[0592] 1000-hour B117 corrosion test

[0593]

[0594] Table 74

[0595] 500-hour B117 corrosion test

[0596]

[0597] In primid-cured polyester powder compositions, isocyanate-based oxazolidinone dieoxy modifiers and acid-functionalized oxazolidinone modifiers based on polyTHF 650 exhibit improved corrosion resistance. Acid-functionalized oxazolidinones can be used to improve corrosion resistance.

[0598] L. Preparation of coating compositions using acid-functionalized oxazolidinones

[0599] Each of the components listed in the table below was weighed in a container and mixed at 3500 RPM for 30 seconds in a prismatic high-speed mixer to form a dry, homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19 mm twin-screw extruder in an active screw configuration at 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 resulted in 45%–55% torque being observed on the equipment. After exiting the extruder, the mixture was dripped onto a set of cooling rollers to cool and re-solidify into solid fragments. The fragments were weighed and 0.15 wt.% Aerosil 200 was added, followed by milling in a Mikro ACM®-1 air classifier mill to obtain a particle size of 5 to 90 micrometers, with most particles being 20 to 50 micrometers and an average particle size of approximately 27–32 micrometers. The resulting coating composition for each example is a free-flowing solid particulate powder coating composition.

[0600] Table 75

[0601] Preparation of powder coatings (in grams)

[0602]

[0603] Application

[0604] The prepared cured powder coating compositions were applied using an Encore Nordson powder coating cup gun under 75 kV, 15 mA limitation, 10 psi atomization, and 10 psi delivery airflow. The coating thickness of the single-coat compositions ranged from 64 µm to 83 µm. The coatings were cured in an electric oven at 350℉ for 20 minutes to form a coating layer.

[0605] test

[0606] According to ASTM B117 Salt Spray Corrosion, a comparative corrosion example was tested by scribing to the center of the panel, exposing the metal on a 4-inch × 6-inch test panel. The panel substrate type and pretreatment are listed along with the corrosion results. After testing, loose coatings and corrosion products on the panel were scraped off under warm water. The scribing creep of the exposed metal and corrosion products was measured as the total scribing creep through the exposed area at a 90° angle to the scribing. The average of five readings from both panels is reported in millimeters, and the total scribing creep is reported in the table below.

[0607] Table 76

[0608] 500-hour B117 corrosion test

[0609]

[0610] Table 77

[0611] 744-hour B117 corrosion test

[0612]

[0613] Table 78

[0614] 1200-hour B117 corrosion test

[0615]

[0616] The results showed that, in single-coat application, acid-functionalized polyester oxazolidinone could improve corrosion resistance compared to unmodified polyester.

[0617] M. Preparation of oxazolidinone coating compositions based on isocyanate prepolymers with epoxy functional groups that react with monobasic acids using polyTHF 650.

[0618] Each of the components listed in the table below was weighed in a container and mixed at 3500 RPM for 30 seconds in a prismatic high-speed mixer to form a dry, homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19 mm twin-screw extruder in an active screw configuration at 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 resulted in 45%–55% torque being observed on the equipment. After exiting the extruder, the mixture was dripped onto a set of cooling rollers to cool and re-solidify into solid fragments. The fragments were weighed and 0.15 wt.% Aerosil 200 was added, followed by milling in a Mikro ACM®-1 air classifier mill to obtain a particle size of 5 to 90 micrometers, with most particles being 20 to 50 micrometers and an average particle size of approximately 27–32 micrometers. The resulting coating composition for each example is a free-flowing solid particulate powder coating composition.

[0619] Table 79

[0620] Preparation of powder coatings (in grams)

[0621]

[0622] test

[0623] According to ASTM B117 Salt Spray Corrosion, a comparative corrosion example was tested by scribing to the center of the panel, exposing the metal on a 4-inch × 6-inch test panel. The panel substrate and pretreatment type are listed along with the corrosion results. After testing, loose coatings and corrosion products on the panel were scraped off under a stream of warm water. The scribing creep of the exposed metal and corrosion products was measured as the total scribing creep through the exposed area at a 90° angle to the scribing. The average of five readings from both panels is reported in millimeters, and the total scribing creep is reported in the table below.

[0624] Table 80

[0625] 1000-hour B117 corrosion test

[0626]

[0627] Table 81

[0628] 1000-hour B117 corrosion test

[0629]

[0630] Table 82

[0631] 1800-hour B117 corrosion test

[0632]

[0633] The results showed that the corrosion resistance of the poly(THF) 650 isocyanate prepolymer diepoxide oxazolidinone, which reacts with a monobasic acid, was improved.

[0634] N. A coating composition was prepared using an oxazolidinone prepolymer made from polyTHF and IPDI, wherein the terminal epoxy group was capped with nonanoic acid and the ring-opening hydroxyl group was reacted with a monoisocyanate.

[0635] Each of the components listed in the table below was weighed in a container and mixed at 3500 RPM for 30 seconds in a prismatic high-speed mixer to form a dry, homogeneous mixture. The mixture was then melt-mixed in a Werner Pfleiderer 19 mm twin-screw extruder in an active screw configuration at 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 resulted in 45%–55% torque being observed on the equipment. After exiting the extruder, the mixture was dripped onto a set of cooling rollers to cool and re-solidify into solid fragments. The fragments were weighed and 0.15 wt.% Aerosil 200 was added, followed by milling in a Mikro ACM®-1 air classifier mill to obtain a particle size of 5 to 90 micrometers, with most particles being 20 to 50 micrometers and an average particle size of approximately 27–32 micrometers. The resulting coating composition for each example is a free-flowing solid particulate powder coating composition.

[0636] Table 82A

[0637] Preparation of powder coatings (in grams)

[0638]

[0639] Application

[0640] The prepared cured powder coating compositions were applied using an Encore Nordson powder coating cup gun under 75 kV, 15 mA limitation, 10 psi atomization, and 10 psi delivery airflow. The coating thickness of the single-coat compositions ranged from 64 μm to 83 μm. The coatings were cured at 375℉ for 20 minutes to form a single coating. The substrates on which the coatings were tested are listed below.

[0641] test

[0642] According to ASTM B117 salt spray corrosion, a comparative corrosion example was tested by scribing to the center of the panel, exposing the metal on a 4 inch × 6 inch B117 corrosion test panel. The panel substrate and pretreatment type are listed along with the corrosion results. After testing, loose coatings and corrosion products on the panel were scraped off under a stream of warm water. The scribing creep of the exposed metal and corrosion products was measured as the total scribing creep through the exposed area at a 90° angle to the scribing. The average of five readings for each B117 panel is given.

[0643] Table 82B

[0644] 1008-hour B117 corrosion test

[0645]

[0646] Table 82C

[0647] 768-hour B117 corrosion test

[0648]

[0649] in conclusion

[0650] The results indicate that, compared with the unmodified control, the B117 salt spray etching of oxazolidinone resins prepared from polyTHF and IPDI prepolymers with terminal epoxy groups capped with nonanoic acid and open-ring hydroxyl groups reacted with monoisocyanates was improved.

[0651] IV. Examples of Liquid Coating Compositions

[0652] A. Preparation of liquid coating compositions using THF 250-based oxazolidinones

[0653] Weigh each of the components listed in the table below in a container and mix under high shear for 20 minutes using a Cowles blade to form a homogeneous mixture. Then, mill the mixture at 3000 RPM for 60 minutes using 0.8–1.2 mm zirconia beads in a horizontal ball mill (Eiger mill, M250VSEEXP). The mill was water-cooled during milling. The fineness of the milled composition was verified to be 6.0 on a Hegman gauge.

[0654] Table 83

[0655] Preparation of liquid coatings (in grams)

[0656]

[0657] In the compositions listed in the table above, methylpentyl ketone is added as a grinding detergent after grinding.

[0658] After grinding, use a low-shear mixing blade to mix the components listed in the table below into the ground composition for 20 minutes.

[0659] Table 84

[0660] Formulation in Example AE

[0661]

[0662] Application

[0663] The prepared liquid coating composition was applied using a 3M Accuspray HG14 spray gun at a misting pressure of 25 psi. The coating thickness was between 65 μm and 85 μm. After a 10-minute flash drying period, the coating was cured at 180℉ for 20 minutes to form a single coat. The substrates on which the coating was tested are listed below.

[0664] test

[0665] According to ASTM B117 salt spray corrosion, a comparative corrosion example was tested by scribing to the center of the panel and exposing the metal on a 4-inch × 6-inch B117 corrosion test. The panel substrate type is listed along with the corrosion results. After testing, loose coatings and corrosion products on the panel were scraped off under a stream of warm water. The scribing creep of the exposed metal and corrosion products was measured as the total scribing creep through the exposed area at a 90° angle to the scribing. The average of eight readings on both panels is reported in millimeters, and the average total scribing creep is reported in the table below.

[0666] Table 85

[0667] 500-hour B117 corrosion test

[0668]

[0669] The adhesion of the composition to an untreated cold-rolled steel substrate was characterized using the standard test method ASTM D3359-22, the tape adhesion test. This method quantifies adhesion based on the proportion of material removed, with a rating from 0 to 5, where 5 represents perfect adhesion.

[0670] Table 86

[0671] Dry adhesion test

[0672]

[0673] The results showed that when a THF-250-based oxazolidinone resin was added to the formulation during the paint mixing stage, B117 salt spray etching corrosion and dry adhesion in the liquid coating were improved.

[0674] B. Preparation of liquid coating compositions using TSR-400-based oxazolidinones

[0675] Weigh each of the components listed in the table below in a container and mix under high shear for 20 minutes using a Cowles blade to form a homogeneous mixture. Then, mill the mixture at 3000 RPM for 60 minutes using 0.8–1.2 mm zirconia beads in a horizontal ball mill (Eiger mill, M250VSEEXP). The mill was water-cooled during milling. The fineness of the milled composition was verified to be 6.0 on a Hegman gauge.

[0676] Table 87

[0677] Preparation of liquid coatings (in grams)

[0678]

[0679] In the compositions listed in the table above, methylpentyl ketone is added as a grinding detergent after grinding.

[0680] After grinding, use a low-shear mixing blade to mix the components listed in the table below into the ground composition for 20 minutes.

[0681] Table 88

[0682] Formulations in Examples L6-L8

[0683]

[0684] Application

[0685] The prepared liquid coating composition was applied using a 3M Accuspray HG14 spray gun at a misting pressure of 25 psi. The coating thickness was between 65 μm and 85 μm. After a 10-minute flash drying period, the coating was cured at 180℉ for 20 minutes to form a single coat. The substrates on which the coating was tested are listed below.

[0686] test

[0687] According to ASTM B117 salt spray corrosion, a comparative corrosion example was tested by scribing to the center of the panel and exposing the metal on a 4-inch × 6-inch B117 corrosion test. The panel substrate type is listed along with the corrosion results. After testing, loose coatings and corrosion products on the panel were scraped off under a stream of warm water. The scribing creep of the exposed metal and corrosion products was measured as the total scribing creep through the exposed area at a 90° angle to the scribing. The average of eight readings on both panels is reported in millimeters, and the average total scribing creep is reported in the table below.

[0688] Table 89

[0689] 500-hour B117 corrosion test

[0690]

[0691] The adhesion of the composition to an untreated cold-rolled steel substrate was characterized using the standard test method ASTM D3359-22, the tape adhesion test. This method quantifies adhesion based on the proportion of material removed, with a rating from 0 to 5, where 5 represents perfect adhesion.

[0692] Table 90

[0693] Dry adhesion test

[0694]

[0695] The results showed that when a THF-250-based oxazolidinone resin was added to the formulation during the paint mixing stage, B117 salt spray etching corrosion and dry adhesion in the liquid coating were improved.

[0696] C. Preparation of liquid coating compositions using IPDI + Eponex 1520-based oxazolidinones

[0697] Weigh each of the components listed in the table below in a container and mix under high shear for 20 minutes using a Cowles blade to form a homogeneous mixture. Then, mill the mixture at 3000 RPM for 60 minutes using 0.8–1.2 mm zirconia beads in a horizontal ball mill (Eiger mill, M250VSEEXP). The mill was water-cooled during milling. The fineness of the milled composition was verified to be 6.0 on a Hegman gauge.

[0698] Table 91

[0699] Preparation of liquid coatings (in grams)

[0700]

[0701] In the compositions listed in the table above, methylpentyl ketone is added as a grinding detergent after grinding.

[0702] After grinding, use a low-shear mixing blade to mix the components listed in the table below into the ground composition for 20 minutes.

[0703] Table 92

[0704] Example AD formulation

[0705]

[0706] Application

[0707] The prepared liquid coating composition was applied using a 3M Accuspray HG14 spray gun at a misting pressure of 25 psi. The coating thickness was between 65 μm and 85 μm. After a 10-minute flash drying period, the coating was cured at 180℉ for 20 minutes to form a single coat. The substrates on which the coating was tested are listed below.

[0708] test

[0709] According to ASTM B117 salt spray corrosion, a comparative corrosion example was tested by scribing to the center of the panel and exposing the metal on a 4-inch × 6-inch B117 corrosion test. The panel substrate type is listed along with the corrosion results. After testing, loose coatings and corrosion products on the panel were scraped off under a stream of warm water. The scribing creep of the exposed metal and corrosion products was measured as the total scribing creep through the exposed area at a 90° angle to the scribing. The average of eight readings on both panels is reported in millimeters, and the average total scribing creep is reported in the table below.

[0710] Table 93

[0711] 500-hour B117 corrosion test

[0712]

[0713] The results showed that when an oxazolidinone resin based on IPDI + Eponex 1510 was added to the formulation during the paint mixing stage, B117 salt spray etching corrosion in the liquid coating was improved.

[0714] V. Examples of Packaging Coating Compositions

[0715] Materials and methods

[0716] The following definitions and methods are used for packaging coating examples.

[0717] Acid value (Acid Number): Determined by titration with a 0.1 M potassium hydroxide (KOH) methanol solution. Acid value is sometimes abbreviated as AV.

[0718] Hydroxyl value (OHV): Measured as the number of mg of KOH equivalent to the number of hydroxyl groups in 1 g of material.

[0719] Molecular weight (Mn): Number average determined by gel permeation chromatography using polystyrene standards according to ASTM D6579-11.

[0720] The viscosity of the aqueous dispersion was measured using a Brookfield viscometer (RV series) with a #4 rotor at 50 rpm and 25°C.

[0721] MEK Friction: The coating is evaluated by the number of rubs required to soften and break it down by hand with a cloth containing saturated methyl ethyl ketone.

[0722] Whitening: This assesses the coating's resistance to erosion by various test solutions. When the coated film absorbs the test solution, it typically becomes cloudy or turns white. Whitening is visually measured using a scale of 1 to 10, where a rating of "10" indicates no whitening and a rating of "0" indicates complete whitening of the film. For commercially viable coatings, a whitening rating of at least 7 is generally expected. Cut the coated panel into 2-inch x 4-inch pieces and immerse half of each piece in the test solution.

[0723] Adhesion: Adhesion testing was performed according to ASTM D 3359 Test Method B using Scotch 610 tape (available from 3M in St. Paul, Minnesota). Adhesion was typically rated on a scale of 0 to 5, where a rating of “5” indicates no adhesion failure.

[0724] Acetic acid: The acetic acid test is designed to measure the coating's resistance to a boiling 3% acetic acid solution. This solution is prepared by mixing 90 grams of glacial acetic acid (a Fisher Scientific product) with 3000 grams of deionized water. The coated strip is immersed in the boiling acetic acid solution for 30 minutes. The strip is then rinsed, cooled in deionized water, dried, and immediately subjected to whitening and adhesion ratings as described above.

[0725] 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 (a product of Dow Chemical) with 3000 grams of deionized water. The coated strips are immersed in the boiling Dowfax solution for 15 minutes. The strips are then rinsed, cooled in deionized water, dried, and immediately subjected to whitening and adhesion ratings as described above.

[0726] The Joy test is designed to measure the resistance of a coating to a hot 180℉ (82°C) detergent solution. The solution is prepared by mixing 30 grams of Ultra Joy concentrated dishwashing liquid (a Procter & Gamble product) with 3000 grams of deionized water. The coated strips are immersed in the 180℉ (82°C) Joy solution for 15 minutes. The strips are then rinsed, cooled in deionized water, dried, and immediately subjected to whitening and adhesion ratings as described above.

[0727] Water boiling: The DI water boiling test is designed to measure the coating's resistance to deionized water vapor. The coated strip is immersed in deionized water and placed in a steam flask at 250℉ (121°C) for 30 minutes. The strip is then cooled in deionized water, dried, and immediately subjected to whitening and adhesion ratings as described above.

[0728] Wedge Bending: The flexibility of the coating is evaluated using a wedge bending test. A coated panel is cut into 2-inch by 4-inch blocks, with the substrate particles extending perpendicular to the length of the cut panel. These blocks are then bent along the length of the panel on a 1 / 8-inch metal rod, with the coated sides facing outwards. The bent sample pieces are then placed on the metal rod, where a wedge shape is pre-cut along the 4-inch length with a taper of 0 to 1 / 8 inch. Once placed in the wedge, each bent sample piece is struck from a height of 12 inches with a 4-pound metal rod to form a wedge shape, with one end of the coated metal striking itself and 1 / 8-inch space remaining on the opposite end. The wedge-bent panels are then immersed in an aqueous solution of copper sulfate and hydrochloric acid containing 1020 g of DI water, 380 g of 6N hydrochloric acid, and 400 g of copper sulfate. The panels are held in the aqueous solution for one minute to intentionally etch areas of coating failure and cracking on the aluminum panel. The etched wedge-shaped curved panel was then examined under a microscope at 10x magnification to determine how far along the bending radius from the impact end the coating cracked. The flexibility results were reported as the length of the cracked region from the impact end or as a percentage of the total length of the wedge-shaped curved panel.

[0729] Thermal feathering: The panel is then cut into 50.8mm x 88.9mm blocks, with the substrate particles extending perpendicular to the long length of the cut panel. The test panel, coated side up, is then inserted into the Carver press between the scribing tool and the anvil. The long edge of the panel rests against the guide block inside the press. The valve on the press base is tightened to clamp the panel into the Carver press. A force of 1500 psi is applied to the hydraulic pressure gauge to create scribing lines simulating a label. The depth of the scribing lines is 0.18 mm.

[0730]

[0731] The above schematic diagram shows a coated panel (100) including scribed lines of a simulated pull tab (102). The simulated pull tab (102) extends perpendicular to the long length (I) of the panel. The endpoints (104, 106) of the scribed lines (which together form the front of the simulated pull tab, i.e., the part where the pull tab is first opened) are all located at the edge of the long length (I) of the panel. The dimensions of the simulated pull tab (102) are: A (48.0 mm); B (11.3 mm); C (24.0 mm); D (18.00 mm); regions E and F (89.4 mm'), and G (10.6 mm). Length D extends from the upper endpoint of the corresponding length C to the left and right vertices of circles E and F, respectively. Length G extends between the upper vertices of circles E and F. The panel is then removed from the press, and two spaced parallel cuts are formed in the panel at the front end of the simulated pull tab along the scribed lines. Each cut begins at the end of the scribe line (104 and 106) and extends perpendicularly inward into the panel. The cuts extend 6.4 mm into the panel along the corresponding portion of the scribe line and are spaced 11.3 mm apart. The panel is then fully immersed in deionized water at 212℉ (100℃) for 10 minutes. The panel is then removed and immediately immersed in deionized water at 22℃ for 2 seconds. The panel is then removed from the deionized water. The cut portion of the simulated pull tab is bent 180° towards the coated surface of the panel. The panel is then inserted into a vise, with the panel held along its length and the edge of the scribe line secured in the vise. The cut portion of the simulated pull tab is then clamped with pliers and pulled 180° across the coated surface of the panel towards the opposite end of the pull tab at a rate of 1 second / cm. The feathering is then measured using a digital microscope. The length of the coating extending to the furthest point of the pull tab opening is measured and recorded in mm.

[0732] A. Polyester acrylic resin

[0733] Polyester 1: The diols, diacids, and catalysts listed in Table 92 were added as batches to a vessel equipped with a steam tower, distillation head, and condenser. The batch temperature was raised to 180°C under continuous stirring at 400 rpm and a nitrogen layer of 0.5 SCFH. The batch temperature was then increased to 230°C in increments of 10°C per hour over a 4-hour period. The steam temperature was continuously monitored, and the batch temperature was not increased at each step until it dropped below 80°C.

[0734] Once the reaction temperature reaches 230°C, check the polymer's acid value (AV) hourly until AV drops below 20. Before this, if the resin becomes transparent, switch from N2 protection to 0.5 SCFH spraying. Once AV is less than 20, switch the spraying back to protection and cool the reaction to 150°C.

[0735] Then, p-hydroxyanisole (MeHQ) was added, followed by maleic anhydride 10 minutes later. The reaction temperature was raised to 220°C, re-injected, and monitored every few hours by manual resin sampling and analysis via AV measurements. Once the acid value dropped below 20, the reaction was cooled to 130°C, and xylene was added through a feed funnel under a nitrogen layer of 0.5 SCFH. After the addition of xylene, the top distillate of the reaction column was switched to an azeotropic distillation apparatus, and additional xylene was added to the attached Dean-Stark water separator. The reactants were reheated to 220°C and again injected with 0.5 SCFH nitrogen.

[0736] The reaction was monitored via AV by collecting xylene resin samples and reducing the solids content of the material to a certain percentage (%). This allowed for comparison with standard bubble tube references (provided by Gardco, and all bubble tube samples cooled to 25°C before analysis). The "cut-off viscosity" was used to assess the degree of polymerization, with the bubble tube viscosity of Z4-Z5 containing 55% solids defined as the primary target. Acid values ​​below 10 were designated as secondary targets. Once the cut-off viscosity was reached, the reaction was sampled to determine the hydroxyl content.

[0737] The resin was cooled to 130°C and Dowanol DPM solvent was added. After 1 hour, the final solvated material was poured out and its acid value and molecular weight were analyzed.

[0738] Table 94

[0739] Polyester prepared in the study

[0740]

[0741] PGA resin 1: Acrylic-modified polyester was formed as follows. The mass of polyester 1 specified in Table 94 was added to a round-bottom flask and sufficient Dowanol DPM was added to reduce the theoretical solids to 59%. The material was heated to 130°C under a nitrogen atmosphere of 0.5 SCFH with continuous stirring at 400 rpm.

[0742] The methacrylic acid monomers shown in Table 95 were premixed and then added over a 40-minute time interval. After 10 minutes, the 87 wt.% initiator shown in Table 95 was diluted with three times its mass of Dowanol DPM. The resulting mixture was then added over a 30-minute time interval. The monomers and initiator were fed separately and simultaneously. The reaction was then maintained at 130°C for 60 minutes. Next, the 13 wt.% initiator shown in Table 95 was diluted with three times its mass of Dowanol DPM. The resulting mixture was then added to the reaction over a 5-minute time interval. A small amount of Dowanol DPM was added to the monomer and initiator funnel, and this volume of liquid was drained into the reaction mixture. The reaction was then maintained at 130°C for 120 minutes. After maintenance, the polyester-grafted acrylic acid (PGA) resin was poured off and the acid value (AV) and molecular weight were analyzed.

[0743] Table 95

[0744] Solvent-based polyester-grafted acrylic (PGA) resin

[0745]

[0746] Aqueous dispersion 1: Aqueous dispersions of PGA resin 1 were formed by heating the resin to 90°C and continuously stirring at 400 rpm while adding dimethylethanolamine under a 0.5 SCFH nitrogen layer. The mixture was stirred for 10 minutes, followed by the addition of preheated deionized water to 60°C over a 30-minute period, ensuring the reaction temperature was maintained above 85°C. The aqueous dispersion was cooled to 45°C and then filtered through a 5 µm filter bag. The solids content and viscosity of the aqueous dispersion were analyzed.

[0747] Table 96

[0748] Aqueous dispersions

[0749]

[0750] B. Oxazolidinone resin

[0751] Oxazolidinone Resin 1:The oxazolidinone-modified resin was formed as follows: 202.3 g of Eponex 1510 (available from Hexion Specialty Chemicals) and 0.72 g of tetrabutylphosphonium bromide (available from Sigma Aldrich) were added to a 1000 mL four-necked flask equipped with an electrically driven stainless steel stirrer, a water-cooled condenser, a nitrogen layer, and a heating mantle with a thermometer connected via a temperature feedback control device. The reaction mixture was heated to 170°C to 175°C. 50 g of isophorone diisocyanate (IPDI, available from Covestro LLC) was added dropwise to the reaction mixture over 1 hour. After addition, the reaction mixture was maintained at 170°C to 180°C until an IR spectrum performed using a ThermoScientific Nicolet iS5 FT-IR spectrometer showed no NCO characteristic band (2269 cm⁻¹). The reaction mixture was then cooled to 120°C and 200 g of Dowanol DPM (available from Dow) was added. The resulting resin was poured off the flask at 80°C. The resin had a solids content of 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 (RI detector) and polystyrene standards. The molecular weights (Mw or Mn) reported herein were determined using this method. Tetrahydrofuran (THF) was used as the eluent at a flow rate of 1 mL / min, and separation was performed using two PL gel-mixed C14 columns.

[0752] Coating formulation: Examples PKG3 through PKG6 were prepared by combining all materials with a stirring blade and mixing for 15 minutes. The coated panels were obtained by applying the coating to 0.0080” Bonderite 702 chromium-pretreated aluminum sheet (AA5182 alloy) using a wire-wound bar to achieve a dry coating weight of approximately 6.5 to 7.0 mg / m² (msi). The coated panels were then immediately placed in a single-zone gas conveyor belt oven for 12 seconds and baked to a peak metal temperature of 465℉ (240.5°C).

[0753] Table 97

[0754] Coating formulation

[0755]

[0756] Table 98

[0757] Cured coating properties

[0758]

[0759] Table 99

[0760] Thermal feathering in Examples 1-4

[0761]

[0762] aspect

[0763] Aspect 1 is a method for synthesizing oxazolidinone compounds according to formula (I):

[0764]

[0765] Wherein R is a linking group containing a polyether, polyester, polyurethane, alkyl, or aromatic functional group; R1 is a terminal group containing a group containing an epoxy, acid, hydroxyl, or amine group, or a non-functional group; R2 is a linking group containing an aromatic or aliphatic functional group; and n is 1 to 500. The method comprises: (i) reacting an isocyanate compound with an epoxy compound in the presence of a catalyst to produce an intermediate compound containing at least two oxazolidinone functional groups linked by R and containing a linking group R2; and (ii) reacting the intermediate compound with a further compound to provide an R1 terminal group to produce the oxazolidinone compound according to formula (I).

[0766] Aspect 2 is the method according to aspect 1, wherein the isocyanate compound is a diisocyanate.

[0767] Aspect 3 is the method according to aspect 1, wherein the isocyanate compound is an isocyanate prepolymer prepared by reacting a polyisocyanate with a polyol in the presence of a polyurethane catalyst.

[0768] Aspect 4 is the method according to aspect 3, wherein the polyol is polytetrahydrofuran and the polyurethane catalyst is dibutyltin dilaurate.

[0769] Aspect 5 is the method according to any one of aspects 1 to 4, wherein the epoxy compound is an aliphatic epoxy compound.

[0770] Aspect 6 is the method according to any one of aspects 1 to 4, wherein the epoxy compound is an aromatic epoxy compound.

[0771] Aspect 7 is the method according to any one of aspects 1 to 6, wherein step (i) is carried out at a temperature of 100°C to 180°C.

[0772] Aspect 8 is the method according to any one of Aspects 1 to 7, wherein the catalyst is present in an amount of 20 ppm to 5000 ppm based on the total weight of the isocyanate compound and the epoxide compound.

[0773] Aspect 9 is a composition comprising an oxazolidinone functional compound according to formula (I):

[0774]

[0775] Where R is a linking group containing polyether, polyester, polyurethane, alkyl, or aromatic functional groups; R1 is a terminal group containing an epoxy, acid, hydroxyl, or amine group, or a non-functional group; R2 is a linking group containing an aromatic or aliphatic functional group; and n is 1 to 500. And the solvent medium.

[0776] Aspect 10 is the composition according to aspect 9, wherein R comprises toluene.

[0777] Aspect 11 is the composition according to aspect 9, wherein R comprises phenyl.

[0778] Aspect 12 is the composition according to aspect 9, wherein R comprises a 1,1,3,-trimethylcyclohexyl group.

[0779] Aspect 13 is the composition according to aspect 9, wherein R comprises a 4,4'-(propane-2,2-diyl)bis(methoxybenzene) group.

[0780] Aspect 14 is the composition according to aspect 9, wherein R1 contains an amine group and the composition is free of epoxy groups.

[0781] Aspect 15 is the composition according to aspect 9, wherein R comprises tolyl or phenyl and R1 is an epoxy group.

[0782] Aspect 16 is a composition according to any one of aspects 9 to 15, wherein the at least two oxazolidinone functional groups are present in an amount of 1 wt.% to 10 wt.% based on the total weight of the compound.

[0783] Aspect 17 is the composition according to any one of aspects 9 to 16, wherein R2 is an aliphatic group.

[0784] Aspect 18 is a composition according to any one of aspects 9 to 17, wherein the compound according to formula (I) has a weight / number average molecular weight of 400 to 10,000.

[0785] Aspect 19 is an electrocoating composition comprising: a cationic film-forming resin; and an additive compound comprising at least two oxazolidinone functional groups, wherein the additive compound has two terminal groups each comprising an amine group, and the additive compound is free of epoxy groups.

[0786] Aspect 20 is the composition according to aspect 19, wherein the additive compound further comprises: at least two linking groups, which comprise and are independently selected from at least one of aromatic groups and aliphatic groups.

[0787] Aspect 21 is the composition according to aspect 20, wherein the linking group is derived from bisphenol A.

[0788] Aspect 22 is the composition according to any one of aspects 19 to 21, wherein the film-forming resin comprises an acrylic resin, an epoxy resin, or a combination thereof.

[0789] Aspect 23 is the composition according to any one of aspects 19 to 22, further comprising a blocked isocyanate crosslinking agent.

[0790] Aspect 24 is the composition according to aspect 23, wherein the crosslinking agent is present in an amount of 25 wt.% to 55 wt.% based on the total weight of the composition.

[0791] Aspect 25 is a composition according to any one of aspects 19 to 24, wherein the amine group is derived from diethylenetriamine or N-methylethanolamine.

[0792] Aspect 26 is a composition according to any one of aspects 19 to 25, wherein the additive compound is present in an amount of 4 wt.% to 10 wt.% based on the total weight of the composition.

[0793] Aspect 27 is a composition according to any one of aspects 19 to 26, wherein the film-forming resin is present in an amount of 50 wt.% to 90 wt.% based on the total weight of the composition.

[0794] Aspect 28 is the composition according to any one of aspects 19 to 27, wherein, after curing to form a coating, the equivalent of these oxazolidinone groups per coating weight is from 100 g / equivalent weight to 1,500 g / equivalent weight.

[0795] Aspect 29 is an article coated with a coating comprising a cured form of a coating composition according to any one of aspects 19 to 28.

[0796] Aspect 30 is a coated article according to aspect 29, wherein the coating exhibits less than 10% scribing creep according to ASTM B117-19.

[0797] Aspect 31 is a coated article according to aspect 29 or 30, wherein the coating exhibits a grade of 4B or higher in the cross-cut adhesion test according to ASTM D3359-22.

[0798] Aspect 32 is a powder coating composition comprising: a film-forming resin; and an additive compound comprising at least two oxazolidinone functional groups separated by a linking group, wherein the linking group is an aromatic functional group.

[0799] Aspect 33 is the composition according to aspect 32, wherein the additive compound further comprises: at least two linking groups, which comprise and are independently selected from at least one of aromatic groups and aliphatic groups; and optionally one or two terminal groups comprising an epoxy group.

[0800] Aspect 34 is the composition according to aspect 32 or 33, wherein the film-forming resin is a polyester-acid resin.

[0801] Aspect 35 is the composition according to any one of aspects 32 to 34, wherein the film-forming resin is a polyester-hydroxy resin.

[0802] Aspect 36 is the composition according to any one of aspects 32 to 35, wherein the film-forming resin is an epoxy resin.

[0803] Aspect 37 is the composition according to any one of aspects 32 to 36, wherein the film-forming resin is an acrylic resin.

[0804] Aspect 38 is the composition according to any one of aspects 32 to 37, wherein the additive compound further comprises a poly-THF backbone.

[0805] Aspect 39 is the composition according to any one of aspects 32 to 38, further comprising a β-hydroxyalkyl-amide crosslinking agent.

[0806] Aspect 40 is the composition according to any one of aspects 32 to 39, further comprising a triglycidyl isocyanurate crosslinking agent.

[0807] Aspect 41 is the composition according to any one of aspects 32 to 40, further comprising a blocked isocyanate crosslinking agent.

[0808] Aspect 42 is the composition according to any one of aspects 32 to 41, further comprising a phenol-based crosslinking agent.

[0809] Aspect 43 is the composition according to any one of aspects 32 to 42, wherein the linking group is derived from bisphenol A.

[0810] Aspect 44 is a composition according to any one of aspects 32 to 43, wherein the additive compound is present in an amount of 1 wt.% to 30 wt.% based on the total weight of the composition.

[0811] Aspect 45 is an article coated with a coating comprising a cured form of a coating composition according to any one of aspects 32 to 44.

[0812] Aspect 46 is a coated article according to aspect 45, wherein the coating exhibits less than 10% scribing creep according to ASTM B117-19.

[0813] Aspect 47 is a coated article according to any one of Aspects 45 or 46, wherein the coating exhibits a thermal conductivity of 0.3 W / mK or higher as measured according to ASTM D7984.

[0814] Aspect 48 is a liquid coating composition comprising: a polyester resin; and an additive compound comprising two oxazolidinone functional groups and at least two terminal groups, the terminal groups comprising and independently selected from at least one of epoxy groups, acid groups, hydroxyl groups, amine groups, aromatic groups and aliphatic groups.

[0815] Aspect 49 is the composition according to aspect 48, wherein the additive compound further comprises: at least two linking groups, which comprise and are independently selected from at least one of aromatic groups and aliphatic groups; and the at least two terminal groups according to aspect 48 comprise hydroxyl-functional aromatic groups.

[0816] Aspect 50 is the composition according to aspect 48 or 49, wherein the film-forming resin is a polyester resin.

[0817] Aspect 51 is the composition according to any one of aspects 48 to 50, further comprising an isocyanate crosslinking agent.

[0818] Aspect 52 is the composition according to any one of aspects 48 to 51, wherein the linking group is derived from bisphenol A.

[0819] Aspect 53 is a composition according to any one of aspects 48 to 52, further comprising a pigment in an amount of 5 wt.% to 40 wt.% based on the total weight of the composition.

[0820] Aspect 54 is a composition according to any one of aspects 48 to 53, further comprising a solvent in an amount of 5 wt.% to 40 wt.% based on the total weight of the composition.

[0821] Aspect 55 is a composition according to any one of aspects 48 to 54, wherein the additive compound is present in an amount of 2 wt.% to 10 wt.% based on the total weight of the composition.

[0822] Aspect 56 is the composition according to any one of aspects 48 to 55, wherein the -OH equivalent weight (EW) of the additive is 300 to 1200 based on the resin solids.

[0823] Aspect 57 is an article coated with a coating comprising a cured form of a coating composition according to any one of aspects 48 to 56.

[0824] Aspect 58 is a coated article according to aspect 57, wherein the coating exhibits at least a 10% reduction in scribing creep according to ASTM B117-19 compared to an article coated with the same oxazolidinone-free coating.

[0825] 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 oxazolidinone functional groups; at least two linking groups comprising aliphatic groups; and two terminal groups comprising epoxy groups.

[0826] Aspect 60 is the composition according to aspect 59, further comprising benzoguanamine, blocked isocyanate or phenolic crosslinking agent.

[0827] Aspect 61 is the composition according to aspect 59 or aspect 60, wherein the additive compound is present in an amount of 1 wt.% to 5 wt.% based on the total resin solids of the coating composition.

[0828] Aspect 62 is the composition according to aspect 60 or aspect 61, wherein the crosslinking agent is present in an amount of 5 wt.% to 20 wt.% based on the total resin solids of the coating composition.

[0829] Aspect 63 is a composition according to any one of aspects 59 to 63, wherein the film-forming resin is present in an amount of 50 wt.% to 95 wt.% based on the total resin solids of the coating composition.

[0830] Aspect 64 is an article coated with a coating comprising a cured form of a coating composition according to any one of aspects 59 to 63.

[0831] Aspect 65 is a coated article according to aspect 64, wherein the coating exhibits 3B or higher adhesion after an acetic acid test according to ASTM D3359-22.

[0832] Aspect 66 is a coated article according to aspect 64 or 65, wherein the coating exhibits a feathering of less than 1 mm after a thermal feathering test.

[0833] Aspect 67 is a coated article according to any one of Aspects 64 to 66, wherein the article comprises a substrate selected from aluminum, tinplate, tin-free steel, food packaging, beverage packaging or metal cans.

[0834] Aspect 68 is a coated article according to any one of aspects 64 to 67, wherein the article is an easy-opening for beverage or food cans.

[0835] Aspect 69 is a method for forming a coated article according to any one of aspects 64 to 67, comprising: coating a substrate selected from aluminum, tinplate, tin-free steel, food packaging, beverage packaging or metal cans with one or more layers of the composition according to any one of aspects 1.

[0836] Aspect 70 is the method according to aspect 69, wherein the substrate is an easy-opening material for beverage or food cans.

[0837] Aspect 71 is the method according to any one of aspects 1 to 8, which is used to form the composition according to any one of aspects 9 to 70.

[0838] Aspect 72 is the composition according to any one of aspects 9 to 18, wherein the additive compound is formed according to the method of any one of aspects 1 to 8.

[0839] Aspect 73 is a composition according to any one of aspects 19 to 31, wherein the additive compound is formed according to any one of aspects 1 to 8.

[0840] Aspect 74 is the composition according to any one of aspects 32 to 47, wherein the additive compound is formed according to any one of aspects 1 to 8.

[0841] Aspect 75 is the composition according to any one of aspects 48 to 58, wherein the additive compound is formed according to any one of aspects 1 to 8.

[0842] Aspect 76 is the composition according to any one of aspects 59 to 70, wherein the additive compound is formed according to any one of aspects 1 to 8.

[0843] Although specific examples of this disclosure have been described above for illustrative purposes, it will be apparent to those skilled in the art that many changes may be made to the details of this disclosure without departing from the scope of the disclosure as defined in the appended claims.

Claims

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

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

3. The method of claim 1, wherein the isocyanate compound is an isocyanate prepolymer prepared by reacting a polyisocyanate with a polyol in the presence of a polyurethane catalyst. R2is a linking group comprising an aromatic functional group or an aliphatic functional group; 4. The method of claim 3, wherein the polyol is polytetrahydrofuran and the polyurethane catalyst is dibutyltin 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 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 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 oxazolidinone functional groups linked by R and comprising a linking group R2 is acid-functionalized prior to step (ii).

10. A powder coating composition comprising: a film-forming resin; and an additive compound comprising at least two oxazolidinone functional groups 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 linking 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 the group consisting of 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 crosslinker. ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ 16. The composition of any one of claims 10-15, further comprising an isocyanuric acid triglycidyl ester crosslinker.

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

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

19. The composition of any one of claims 10-18, wherein the linking group is derived from bisphenol A.

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

Images