Emulsifiable resins

Abstract

A composition that includes an aqueous dispersion that includes an aqueous medium as a continuous phase and a dispersed phase that includes a polyurethane resin and a hydrophobic component that can include a hydrophobic crosslinker and / or a hydrophobic catalyst.

Description

EMULSIFIABLE RESINSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority of prior U.S. Provisional Applications under 35 U.S.C. 119 Serial Nos. 63 / 767,190, filed March 5, 2025, titled “Emulsifiable Resins”, 63 / 565,264, filed March 14, 2024, titled “High Solids Coating Compositions”, and 63 / 565,239, filed March 14, 2024, titled “Controlled Cure Coating Compositions” which are incorporated herein by reference.FIELD

[0002] The present disclosure relates to a composition including a polyurethane resin and a hydrophobic component.BACKGROUND

[0003] Coatings can be applied to a wide variety of substrates to provide color and other visual effects, corrosion resistance, abrasion resistance, chemical resistance, and the like. In addition, various types of coatings, such as coatings applied to packaging, automotive and a wide variety of substrates, can be formed from compositions that can be cured to form coating layers.SUMMARY

[0004] The present disclosure provides a composition that includes an aqueous dispersion includes an aqueous medium as a continuous phase and a dispersed phase that includes a polyurethane resin and a hydrophobic component that can include a hydrophobic crosslinker and / or a hydrophobic catalyst.DETAILED DESCRIPTION

[0005] The present disclosure provides a composition, that may be curable, and which may alternatively be referred to as a coating composition, and a method of making. The composition of the present disclosure exhibits high solid content and a low viscosity.I. Definitions

[0006] For purposes of the following detailed description, it is to be understood that the disclosure may assume various alternative variations and step sequences, except whereexpressly specified to the contrary. Moreover, other than in any operating examples or where otherwise indicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term "about." For example, numerical ranges provided for weight percentages of components or amounts of components added should be construed as being modified by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0007] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard variation found in their respective testing measurements.

[0008] Also, it should be understood that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of "1 to 10" is intended to include all sub-ranges from (and including) the recited minimum value of 1 to the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.

[0009] The use of the singular includes the plural and plural encompasses singular, unless specifically stated otherwise. In addition, the use of "or" means "and / or" unless specifically stated otherwise, even though "and / or" may be explicitly used in certain instances.

[0010] ‘ ‘Acid value on solids,” when used herein, indicates a quantified acidity of a given chemical substance based on the milligrams (mg) of potassium hydroxide (KOH) required to neutralize the acidic constituents in 1 gram of the non-volatile components.

[0011] Unless otherwise indicated, ambient conditions of temperature and pressure are ambient temperature (20-25°C, such as 23°C) and standard pressure of 101.3 kPa (1 atm) at a relative humidity in the air of 35% to 75%, such as 55%.

[0012] As used herein, the term “aqueous dispersion” refers to a dispersion where the continuous phase includes at least 30 wt. %, such as at least 50 wt. % water based on the total weight of the continuous phase.

[0013] As used herein, the terms “aqueous dispersibility” and “water dispersibility”, and similar terms, refer to the property of a material, when 1 gram of the material is added to 100 ml of an aqueous medium or water, to form a dispersion that either does not separate and / or coalesce after three hours at ambient conditions or if some separation occurs within three hours at ambient conditions, returns to an aqueous dispersion form upon stirring.

[0014] As used herein, the term “basecoat” refers to a coating layer that is applied onto a primer coat, another basecoat layer; and / or directly onto a substrate, optionally including components (such as colorants) that impact the color and / or provide other visual impact. A clearcoat may be applied over the basecoat layer.

[0015] As used herein, the term “binder” refers to elements of a coating composition that hold the ingredients of a coating composition together. Binders can include, without limitation, acrylic polymers, polyurethanes, polyesters, epoxy polymers, melamine resins and alkyd polymers.

[0016] As used herein, the terms “crosslinker”, “reactant” and similar terms refer to a molecule that includes at least one functional group that is reactive with a group in another molecule in a curable composition, such as a polyurethane, such as, without limitation, epoxy, (meth)acrylate, isocyanate, aminoplast, aziridine and / or carbodiimide.

[0017] As used herein the terms “cure” and “curing” refer to the use of a compound (a “curing agent”) that is able to participate in a chemical reaction that results in crosslinking and / or polymerization between monomers, oligomers, pre-polymers and / or polymers.

[0018] As used herein the terms “curing agent”, “crosslinker”, and “crosslinking agent” refer to compounds that are able to participate in a chemical reaction that results in crosslinking and / or polymerization between monomers, oligomers, pre-polymers and / or polymers.

[0019] As used herein the term “direct gloss topcoat” refers to a coating layer, applied over at least a portion of a substrate or another coating layer that can impart a decorative and / or protective finish to a substrate.

[0020] As used herein, the term “film-forming components” refers to constituents of a coating composition and can include polymers, resins, crosslinking materials or any combination thereof that are part of the film-forming mechanism of the coating composition. Film-forming components can be dried or cured, as nonlimiting examples, by exposure to elevated temperatures (for example, above 40 °C), actinic radiation or under ambient conditions.

[0021] As used herein, the terms “flash” or “flash off refers to removal of solvents, that allow an applied coating composition to remain in a liquid state, to evaporate.

[0022] As used herein, the term “hydrophobic component” refers to a compound that includes at least 50 wt.%, based on the weight of the compound, of one or more molecules that have a solubility in deionized water of less than 5 mg / ml at ambient conditions.

[0023] “Isocyanate equivalent weight” and “NCO equivalent weight” as used herein refers to, unless otherwise stated, the isocyanate (NCO) equivalent weight (in grams per equivalent; g / eq) determined using ASTM D2572-19 (Standard Methods of Isocyanate Groups in Urethane Materials or Prepolymers) revised as described herein.

[0024] As used herein, the terms “flash” or “flash off’ refers to removal of solvents, that allow an applied coating composition to remain in a liquid state, to evaporate.

[0025] As used herein, the term (meth) acrylate” is intended to include both methacrylates and acrylates, nonlimiting examples include esters of acrylic acid and esters of methacrylic acid.

[0026] As used herein, the term “monocoat” refers to a coating layer, which can be a single coating layer, such as a topcoat, used to finish a surface of a substrate and not followed by the application of another coating layer, such as a clearcoat.

[0027] As used herein, the terms “Multi-functional” and “Difunctional”, refers to a molecule having more than two, or two functional groups, respectively, as a nonlimiting example, when used in connection with isocyanate, meaning that more than one isocyanate functionality is present per molecule.

[0028] Unless otherwise indicated, as used herein, the term "molecular weight" refers to a weight average molecular weight (“Mw”) as determined by gel permeation chromatography (GPC) using appropriate polystyrene standards. If a number average molecular weight (“Mn”) is specified, the weight is determined in the same GPC manner, while calculating a number average from the thus obtained polymer molecular weight distribution data. As a nonlimiting example, Mn refers to the total weight of a material divided by the number of molecules in the material and can be determined using gel permeation chromatography. Unless otherwise noted, Mw and Mn are in units of g / mol.

[0029] As used herein the term “organic solvent” refers to carbon containing molecules, nonlimiting examples including esters, ketones, glycol ethers, alcohols, hydrocarbons and mixtures thereof that are capable of dissolving or dispersing other substances at ambient conditions.

[0030] As used herein the prefix “poly” refers to two or more. As a nonlimiting example, a polyisocyanate refers to a compound that includes two or more isocyanate groups and a polyol refers to a compound that includes two or more hydroxyl groups.

[0031] “Polymer” and “Polymeric” refer to oligomers, polymers, homopolymers (e.g., prepared form a single monomer species), copolymers (e.g., prepared form at least two monomer species), terpolymers (e.g., prepared from at least three monomer species), and graft polymers.

[0032] As used herein, the term “primer” refers to an undercoating layer that can be applied onto a substrate in order to prepare the surface for application of a protective or decorative coating composition.

[0033] “Resin solids” refers to the non-volatile components that make up the binder or filmforming components of the composition. As used herein, a weight percentage based on “resin solids” refers to an amount of a component based on a total weight of the binder or film-forming components of a composition.

[0034] As used herein, the terms “solids”, “total solids” and “total resin solids” refers to the non-volatile components present in a composition of volatile and non-volatile components. As used herein, a weight percentage based on “solids” “total solids” and / or “total resin solids” refers to an amount of a component based on a total weight of the non-volatile components of a composition determined by comparing an initial sample weight with a final sample weight after exposure to 110 °C for one hour. “High solids” refers to a composition having a solids level of at least 25 wt. % based on the weight of the composition.

[0035] As used herein, the term “solvent” refers to a substance capable of dissolving or dispersing other substances at ambient conditions.

[0036] As used herein, the term “surfactant” refers to a substance that, when added to a liquid, reduces its surface tension, thereby increasing its spreading and wetting properties.

[0037] As used herein the term “topcoat” refers to a coating layer, applied over at least a portion of another coating layer.

[0038] The present disclosure provides a composition, that may be a curable composition, which may alternatively be referred to as a coating composition. The composition includes an aqueous dispersion that includes a polyurethane. The polyurethane resins described herein enable emulsification of hydrophobic moieties allowing for increased solids and / or lower viscosity compared to compositions that do not have the disclosed emulsifying property.

[0039] The present disclosure provides an aqueous dispersion that includes a polyurethane resin and a hydrophobic component. Optionally, the hydrophobic component can be a separate component wherein that does not form a covalent bond with the polyurethane resin. The polyurethane resin may include a water dispersible group, wherein the water dispersible groupmay include ionic groups and / or non-ionic groups, such as an acid group, a polyether group, a non-reactive amine group, a hydroxyl group, a thiol group and / or the like.

[0040] The hydrophobic component may include 0.01 wt. % to 70.00 wt. % such as 1 wt. % to 60 wt. % of the total resin solids of the composition.

[0041] As used herein, the phrase “wt. %” refers to weight percent.II. Polyurethane Resin

[0042] The polyurethane resin can be used as a binder or film-forming resin in curable compositions and can be prepared using methods known in the art. The polyurethane can be prepared by reacting an isocyanate reactive compound, such as, without limitation, hydroxyl functional compounds, thiol or mercapto functional compounds, and / or primary or secondary amines, with a polyisocyanate. The polyurethane resins may be nonionic or ionic and may include functional groups, such as acid groups, hydroxyl groups, thiol groups, alkyl groups, and / or reactive amine groups or may be free of functional groups. The functional groups can aid in the aqueous dispersibility of the polyurethane resin.

[0043] The polyurethane resin may have a weight average molecular weight greater than 800 g / mol and a number average molecular weight (Mn) of at least 400 g / mol, such as at least 500 g / mol, or at least 1000 g / mol, at least 1000 g / mol, or at least 2000 g / mol, or at least 3000 g / mol and up to 50,000 g / mol g / mol, such as up to 40,000 g / mol, or up to 30,000 g / mol, or up to up to 5000, or within any range using any two of the foregoing values as endpoints, such as from 400 g / mol to 50,000 g / mol, or from 500 g / mol to 40,000 g / mol, or from 1000 g / mol to 30,000 g / mol, as determined by gel permeation chromatography using polystyrene standards.

[0044] The composition, which may be a curable composition, of the present disclosure may include an amount of polyurethane resin ranging from 1 wt. %, such as from 5 wt. %, or from 30 wt. %, or from 40 wt. %, or from 50 wt. %, or from 60 wt. % up to 70 wt. %, such as up to 80 wt. %, or up to 85 wt. %, or within any range using any two of the foregoing values as endpoints, such as from 1 wt. % to 85 wt. %, or from 5 wt. % to 80 wt. %, or from 30 wt. % to 70 wt. %, where wt. % is based on total resin solids. i. Polyisocyanate

[0045] The polyurethane of the present disclosure may be derived from a polyisocyanate, such as a diisocyanate, and as a nonlimiting example, reactive with isocyanate reactive compounds.

[0046] Suitable polyisocyanates may be aliphatic, aromatic, cycloaliphatic or heterocyclic isocyanates. Suitable aliphatic isocyanates may include trimethylene, tetramethylene, pentamethylene, hexamethylene, 1 ,2-propylene, 1,2-butylene, 2,3-butylene and 1,3-butylene diisocyanates; the cycloalkylene compounds such as 1,3-cyclopentane, 1 ,4-cyclohexane, 1,2- cyclohexane diisocyanates and isophorone diisocyanates; the aromatic compounds such as m- phenylene, p-phenylene, 4,4’-diphenyl, 1,5-naphthalene and 1 ,4-naphthalene diisocyanates; the aliphatic-aromatic compounds such as 4,4'-diphenylene methane, 2,4- or 2,6-tolylene, or mixtures thereof, 4,4'-toluidine, tetramethyl xylylene, and xylylene diisocyanates; the nuclear- substituted aromatic compounds such as dianisidine diisocyanate, 4,4'-diphenylether diisocyanate and chlorodiphenylene diisocyanate; the triisocyanates such as triphenyl methane- 4,4’,4"-triisocyanate, 1,3,5-triisocyanato benzene, hexamethylene diisocyanate isocyanurate trimer, and 2,4,6-triisocyanato toluene; and the tetraisocyanates such as 4,4'-dimethyldiphenyl methane-2,2',5,5'-tetraisocyanate; the polymerized polyisocyanates such as tolylene diisocyanate dimers and trimers, and the like.

[0047] Suitable diisocyanates also include diisocyanates having a single aromatic or cycloaliphatic ring such as isophorone diisocyanate (IPDI), tetramethyl xylene diisocyanate (TMXDI), 4,4’ -methylene dicyclohexyl diisocyanate (H12MDI), 1,6-hexamethylene diisocyanate (HDI), l,3-bis(isocyanato methyl)cyclohexane, l,5-diisocyanato-2- methylpentane, 1 ,6-diisocyanato-2,2,4-trimethylhexane, 1 ,6-diisocyanato-2,4,4- trimethylhexane, 1,4-diisocyanatobutanone, tri-methyl-hexamethylene diisocyanate, 1,8- diisocyanatooctane, 1,12-diisocyanatododecane, l,8-diisocyanto-2,4-dimethyloctane, 1,4- bis(isocyanato methyljcyclohexane, trans- 1 ,4-cyclohexylene diisocyanate, and 2,4- diisocy anato- 1 -methyl cyclohexane.

[0048] Other suitable aliphatic diisocyanates may also include, methyl-2,6- diisocyanatohexanoate, bis(isocyanatomethyl)cyclohexane, 1,3- bis(isocyanatomethyl)cyclohexane, 2,5(6)-bis(isocyanatomethyl)cyclo[2.2.1.]heptane, 1,3,3- trimethyl- 1 -(isocyanatomethyl)-5 -isocyanatocyclohexane, octahydro-4, 7-methano- 1H- indenedimethyl diisocyanate, and l,l’-methylenebis(4-isocyanatocyclohexane). ii. Isocyanate Reactive Compounds

[0049] The polyurethane of the present disclosure may be formed from an isocyanate reactive compound, such as primary or secondary amine functional compounds, thiol functional compounds, hydroxyl functional compounds reactive with an isocyanate of the polyisocyanate. The hydroxyl functional compound may be, without limitation, hydroxyl functional polyesters,polycarbonates, polyethers, polyether amines, such as those available under the trade name Jeffamine available from Huntsman International LLC, or acrylic polymers. Thiol functional compounds can include, without limitation, C2-C20 alkyl dithiols, such as dodecanedithiol.

[0050] The hydroxyl groups of the hydroxyl functional compound may be connected by a bridging group selected from: an alkylene group; an alkenylene group; an alkynylene group; or an arylene group. The hydroxyl functional compound may lack acid groups, such as a nonacid containing polyol.

[0051] Hydroxyl functional compounds include, but are not limited to alkylene glycols, such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol and neopentyl glycol; hydrogenated bisphenol A; cyclohexanediol; propanediols including 1 ,2-propanediol, 1,3-propanediol, butyl ethyl propanediol, 2-methyl-l,3-propanediol, and 2-ethyl-2-butyl- 1,3- propanediol; butanediols including 1,4-butanediol, 1,3-butanediol, and 2-ethyl-l,4-butanediol; pentanediols including trimethyl pentanediol and 2-methylpentanediol; cyclohexanedimethanol; hexanediols including 1 ,6-hexanediol, caprolactonediol (such as the reaction product of epsilon-capro lactone and ethylene glycol), hydroxyalkylated bisphenols; polyether glycols, such as poly(oxytetramethylene) glycol and polytetrahydrofuran; trimethylol propane; pentaerythritol; di-pentaery thritol; trimethylol ethane; trimethylol butane; dimethylol cyclohexane; glycerol and the like or combinations thereof.

[0052] The hydroxyl functional compound may be a non-acid containing polyol, meaning the polyol lacks acid groups.

[0053] Hydroxy functional polyesters, poly(meth)acrylates, and polycarbonates may be suitable hydroxyl functional compounds reactive with the polyisocyanate in the formation of the polyurethane resin. As used herein and as will be understood by one skilled in art the term "(meth)acrylate" denotes both the acrylate and the corresponding (meth)acrylate. The poly(meth)acrylate can be any suitable poly(meth) acrylate and mixtures thereof. The poly(meth)acrylate may include di(meth)acrylate, tri(meth)acrylate, tetra(meth)acrylate, and / or one or more other ethylenically unsaturated radically polymerizable monomers. Mixtures of poly(meth)acrylate monomers may also be used, including mixtures of mono, di, tri, and / or tetra (meth)acrylate.

[0054] Hydroxy functional compounds include, but are not limited to the following: ethylene glycol; 1,2-propane diol; 1,3-propane diol; 1,2-butandiol; 1,3-butandiol; 1,4-butandiol; but-2- ene 1,4-diol; 2,3-butane diol; 2-methyl 1,3-propane diol; 2,2'-dimethyl 1,3-propanediol (neopentyl glycol); 1,5 pentane diol; 3-methyl 1,5 -pentanediol; 2,4-diethyl 1,5-pentane diol;1,6-hexane diol; 2-ethyl 1,3-hexane diol; diethylene glycol; triethylene glycol; dipropylene glycol; tripropylene glycol; 2,2,4-trimethyl pentane 1,3-diol; 1,4 cyclohexane dimethanol; tricyclodecane dimethanol; 2,2,4,4-tetramethyl cyclobutane 1,3-diol; isosorbide; 1,4- cyclohexane diol; l,T-isopropylidene-bis (4-cyclohexanol); and mixtures thereof.

[0055] Suitable hydroxy functional compounds may include polyether diols such as Terathane® 250 and Terathane® 650 available from Invista or the PolyTHF® polyether diols available from BASF.A. Acid Functional Polyurethane Resins

[0056] When acid functional polyurethane resins are used, the polyurethane resin can be prepared, without limitation, by incorporation of acid containing polyols, hydroxy acids, such as hydroxy pivalic acid, and / or mercapto acids, such as 3 -mercaptopropionic acid.

[0057] As a nonlimiting example, the acid functional polyurethane can be prepared by reacting a polyester polyol, polycarbonate polyol, polyether polyol or acrylic polyol with a polyisocyanate and an acid functional polyol (such as dimethylol propionic acid) such that the NCO / OH stoichiometric ratio is greater than 1: 1 to generate an NCO functional prepolymer. The terminal isocyanates can then be reacted with a non-tertiary aminoalcohol such as diethanolamine or ethanolamine to produce a terminal OH functional polymer. Some or all of the terminal OH groups may then be reacted with anhydrides such as succinic anhydride or methylhexahydrophthalic anhydride to produce a polyurethane with terminal COOH groups. The acid groups introduced in the first stage of urethane preparation are considered to be internal COOH groups, while the acid groups introduced after reaction of the anhydride with aminoalcohol are considered to be terminal COOH groups. The acid functional polyurethane polymers may be neutralized with a tertiary alkylated amine prior to and / or after contact with water to provide water dispersibility.

[0058] As an alternative nonlimiting example, a terminal isocyanate group can be reacted with an acid monomer. The acid groups introduced in the first stage of urethane preparation are considered to be internal COOH groups, while the acid groups introduced after reaction with the acid monomer are considered to be terminal COOH groups. The acid functional polyurethane polymers may be neutralized with a tertiary alkylated amine prior to and / or after contact with water to provide water dispersibility (a uniform distribution of acid functional polyurethane in water).

[0059] An acid functional polyurethane can also be formed, without limitation, by utilizing a ring opening of a cyclic anhydride. This can be done by forming a prepolymer from anisocyanate, an isocyanate reactive compound such as a non-acid containing polyol, an acid containing polyol, and / or combinations thereof. After formation of the prepolymer, a reactive amine including hydroxyl groups and / or polyol may be added to react with the remaining unreacted isocyanate groups sequentially an anhydride may be reacted with hydroxyl groups of the prepolymer, and a neutralizing amine may be used to disperse the polyurethane into water.

[0060] The polyurethane may also be formed, without limitation, from an excess of isocyanate, an isocyanate reactive compound such as, without limitation, an acid containing polyol, and optionally a non-acid containing polyol. The prepolymer may then be reacted with a non-acid containing isocyanate reactive compound which may include hydroxyl groups, thiol groups, and / or non-tertiary amine groups and may be followed by reacting with a neutralizing amine to disperse the polyurethane into water.

[0061] The polyurethane may also be formed, without limitation, by incorporating an acid onto the polyurethane resin. A prepolymer may be formed from an isocyanate, an isocyanate reactive compound such as an acid containing polyol, a non-acid containing polyol, and / or combinations thereof. An acid monomer may then be reacted with the remaining isocyanate groups of the prepolymer, and a neutralizing amine may be used to disperse the polyurethane into water.

[0062] The acid functional polyurethane resin can have an acid value on solids greater than 8, such as greater than 10, such as greater than 13, or greater than 15 or greater than 25 mg KOH / g on resin solids and can be up to 150, such as up to 140, or up to 130 mg KOH / g on resin solids, or within any range using any two of the foregoing values as endpoints, such as from 10 mg KOH / g to 150 mg KOH / g, of from 13 mg KOH / g to 140 mg KOH / g, or from 15 mg KOH / g to 130 mg KOH / g. The acid value of the acid functional polyurethane resin may be determined using a Metrohm 798 MPT Titrino automatic titrator, manufactured by Metrohm AG, according to ASTM D4662-15. The value may be then divided by the content of solids to result in acid value on solids. The acid groups of the polyurethane may be neutralized to enable aqueous dispersion of the polyurethane.B. Nonionic Polyurethanes

[0063] Nonionic polyurethanes can include nonionic functional groups or be free or essentially free of functional groups. Functional nonionic polyurethanes can be prepared by first reacting an isocyanate reactive compound with a polyisocyanate such that the NCO / isocyanate reactive group ratio is greater than 1:1 to generate an NCO functional prepolymer.The terminal isocyanates can then be reacted with a compound having multiple isocyanate reactive groups to provide functional nonionic polyurethanes. As an alternative, functional nonionic polyurethanes can be prepared by first reacting an isocyanate reactive compound with a polyisocyanate such that the NCO / isocyanate reactive group ratio is less than 1 : 1 to generate a polyurethane with non-NCO functional nonionic groups. Nonionic polyurethanes can include hydroxy, thiol and / or amine functional groups that can aid in the aqueous dispersibility of the polyurethane resin. i. Thiol Functional Polyurethanes

[0064] The polyurethane resins of the present disclosure contain thiol functional groups. Poly thiol or mercapto compounds as well as compounds that include both thiol or mercapto groups and hydroxy functional groups may be suitable compounds that can be reactive with isocyanate groups of the NCO functional prepolymer in the formation of the polyurethane resin.

[0065] Suitable poly thiol or poly mercapto compounds may include, without limitation, C2- C20 alkyl dithiols, such as dodecanedithiol, trimethylolpropane tris(2-mercaptoacetate), trimethylolpropane tris(2-mercaptopropionate), 1,8- dimercapto-3,6-dioxaoctane, thiol terminated polyethers, pentaerythritol-tetrakis-3-mercapto propionate, pentaerythritol-tetrakis- 2-mercapto acetate, 2,3-bis((2-mercaptoethyl)thio)-l-propanethiol, 2,3-dithio (2-mercapto)-l- propane mercaptan and thiol-terminated polyethers.

[0066] Suitable compounds that include both thiol or mercapto groups and hydroxy functional groups may include, without limitation, dithiothreitol; thiol and hydroxy functional polyesters, poly(meth)acrylates, and polycarbonates; 2,3-dimercapto - 1 - propanol, and compounds according to the formula:(HS)x-R1y-(OH)zwhere R1can be at least C2 , such as C3 or Cr, to C20 linear, branched or cyclic, aliphatic and / or aromatic group or a polymeric backbone that can include O, N and / or S hetero atoms, where y is from 1 to 100, such as 1 to 50 or 1 to 25; x can be from 1 to 50, such as 1 to 30 or 1 to 20 or 1 to 10 or 1 to 5, where the SH group is bonded to a carbon atom; and z can be from 0 to 60, such as 1 to 40 or 1 to 30 or 1 to 20 or 1 to 10 or 1 to 5, where the OH group is bonded to a carbon atom.

[0067] The polyurethane containing thiol functional groups may be derived from a mixture comprising a polyisocyanate and an amount of compounds that include thiol or mercaptogroups of from 15 wt. %, such as from 20 wt. %, or from 25 wt. % to 30 wt. %, such as 35 wt. %, or 40 wt. %, or 50 wt. %, or 60 wt. %, or 70 wt. % or within any range using any two of the foregoing values as endpoints, such as from 15 wt. % to 70 wt. %, such as from 20 wt. % to 60 wt. %, or from 25 wt. % to 50 wt. %, where wt. % is based on total resin solids of the mixture. ii. Hydroxy Functional Polyurethanes

[0068] Hydroxy functional nonionic polyurethanes can be prepared as described above, where the hydroxyl functional compound can include, without limitation, the hydroxyl functional polyesters, polycarbonates, polyethers and / or polyols listed above. iii. Amine Functional Polyurethanes

[0069] Amine functional nonionic polyurethanes can be prepared as described above, where the amine functional compound can include, without limitation, primary or secondary amine functional compounds such as amine functional polyesters, polyether amines, non-tertiary aminoalcohols such as diethanolamine or ethanolamine, and diamines such as the alkyl diamines such as ethylenediamine, diaminobutane and diaminohexane.III. Aqueous Dispersion

[0070] The aqueous dispersion includes one or more of the above described polyurethanes dispersed in an aqueous medium. The aqueous dispersion may include an aqueous medium wherein the solvent includes at least 30 wt. % water, such as at least 40 wt. % water, such as at least 50 wt. % water. The aqueous dispersion may include a dispersed phase including a polyurethane resin and a hydrophobic component and a continuous phase including the aqueous medium.IV. Hydrophobic Component

[0071] The hydrophobic component may include a reactant, such as a crosslinker, and / or a catalyst. The hydrophobic component may include a reactant that is reactive with the polyurethane and / or other components of the present composition. The reactant may include one or more reactive functional groups. The reactive functional groups may include epoxy, (meth)acrylate, isocyanate, aminoplast, aziridine and / or carbodiimide. The reactant may be referred to as a crosslinker, especially when the reactant includes more than one reactive functional group.

[0072] The hydrophobic component may include 0.01 wt. % to 70.00 wt. % such as 1 wt. % to 60 wt. % of the total resin solids of the composition.

[0073] The crosslinker may include functional groups utilized in a molar ratio of crosslinker functional groups to functional groups of the polyurethane resin of from 0.25:1.75, such as from 0.5: 1.5 or from 0.75:1.25, or from 0.17:1.1, or from 0.75:1, or from 0.5:1 or any ratio within the range of the foregoing ratios, such as from 0.25: 1.75 to 0.5:1.

[0074] The composition can have a crosslinker in an amount of from 10 wt. %, such as from 15 wt. %, or from 30 wt. %, or from 40 wt. %, and up to 70 wt. %, such as up to 60 wt. %, or up to 50 wt. %, or within any range using any two of the foregoing values as endpoints, such as 10 wt. % to 70 wt. %, or from 15 wt. % to 60 wt. %, or from 30 wt. % to 60 wt. %, or from 40 wt. % to 50 wt. %, where wt. % is based on the total resin solids weight of the coating composition.

[0075] The catalyst may include an organometallic and / or an inorganic catalyst. Organometallic catalysts include, but are not limited to, catalysts having a carbon-metal bond, dibutyltin catalysts, zinc catalysts, tin catalysts, titanium catalysts, zirconium catalysts, and the like. The catalyst may include an organic catalyst, including, but not limited to, an amine, quaternary ammonium compounds, phosphonium containing compounds, quaternary phosphonium group containing compounds, and the like. The catalyst may include a hydrophobic bismuth catalyst such as bismuth neodecanoate.

[0076] Conventional aqueous compositions may be unable to effectively utilize many catalysts such as bismuth catalysts, as the catalysts are incompatible with water-based compositions or aqueous dispersion. The present disclosure addresses one or more issues with conventional compositions by providing an effective emulsifier resin wherein the addition and level of catalyst may be controlled and tuned to a specific need. Conventional compositions may associate the catalyst level with a resin vehicle which restricts the possible formulations.

[0077] The composition can include the catalyst in an amount of from 0.1 wt. %, such as from 0.5 wt. %, or from 1 wt. %, up to 5 wt. %, such as up to 4.5 wt. %, or up to 4 wt. %, or up to 2 wt. %, or up to 1.1 wt. % or within any range using any two of the foregoing values as endpoints, such as from 0.1 wt. % to 5 wt. %, or from 0.1 wt. % to 4.5 wt. %, or from 0.5 wt. % to 4 wt. %, where wt. % is based on the resin solids weight of the coating composition. For example, if a composition included 100 g of resin solids, a catalyst amount of 1 wt. % would be 1 g of catalyst.

[0078] The composition can include, optionally as part of the hydrophobic component, other additives, including, but not limited to, a surfactant, a surface agent, a plasticizer, anantioxidant, a hindered amine light stabilizer, a UV light absorber and / or stabilizer, a flow control agent, a thixotropic agent, a filler, a reactive diluent, a leveling agent, a defoamer, a grind vehicle, a colorant such as a pigment or dye, and other additives known to those skilled in the art.

[0079] The aqueous dispersion may include a film-forming component including a binder and a crosslinking agent.

[0080] The present disclosure provides methods of coating a substrate. The general method includes applying a composition of the present disclosure over at least a part of a substrate using draw down coating, spray coating, roller coating, coil coating, dip coating, precision coating, electrodeposition coating or spin coating techniques. The method may then include curing the composition to form a cured layer on the substrate. The emulsifying property of the composition can allow catalyst to be released for cure of the coating. The composition may be cured at a temperature of from 10 °C to 210 °C for from 5 seconds to 168 hours.

[0081] Prior to curing the applied curable composition, the composition may be flashed at a temperature of from 10 °C to 40 °C for from 0 minutes to 60 minutes.

[0082] As indicated herein, the substrate can include a previously applied coating layer. As a nonlimiting example, the present coating composition can become part of a multilayer coating composition. As nonlimiting examples, the present coating composition can be a coating layer applied over a basecoat or a coating layer applied over a primer coat.

[0083] Depending on the particular use intended, the present coating composition can be applied as a primer, a basecoat, a topcoat, such as a clearcoat, or it can be applied as a direct gloss topcoat or monocoat.

[0084] Application of the present coating composition can result in a coating layer that has a dry film thickness of from 0.5 pm to 250 pm, such as from 0.5 pm to 200 pm, or from 0.5 pm to 150 pm, or from 0.5 pm to 100 pm, or from 0.5 pm to 75 pm, or from 0.5 pm to 65 pm, or from 0.5 pm to 55 pm, or from 0.5 pm to 52 pm, or from 1 pm to 250 pm, or from 1 pm to 200 pm, or from 1 pm to 100 pm, or from 1 pm to 65 pm, or from 1 pm to 60 pm, or from 1 pm to 55 pm, or from 5 pm to 250 pm, or from 5 pm to 200 pm, or from 5 pm to 100 pm, or from 5 pm to 65 pm, or from 5 pm to 60 pm or from 5 pm to 55 pm measured according to ASTM D7091-21.

[0085] The composition of the present disclosure may include multiple components, wherein one component includes the polyurethane and a different component that includes the hydrophobic component. The composition may include multiple components, wherein one component includes the polyurethane and the hydrophobic component and a differentcomponent includes a film-forming component. Prior to application, the components of the multiple component composition are combined and then applied to a substrate.

[0086] The composition of the present disclosure may include one component (IK), wherein the one component includes the polyurethane and the hydrophobic component.

[0087] The coating compositions described herein can be applied, as a nonlimiting example, by forming a coating layer on at least a portion of a substrate. The method can include applying the present coating composition over at least a portion of the substrate; and exposing the coating composition to a sufficient amount of energy for a sufficient amount of time for the coating composition to cure, such as the reaction of the polyurethane resin and / or other film-forming components and the crosslinker.

[0088] The coating composition can be applied using methods known in the art, such as spray application, draw down, brush application, dip application and / or precision application.

[0089] As indicated above, the substrate can include a previously applied coating layer. As a nonlimiting example, the present coating composition can become part of a multilayer coating composition. As nonlimiting examples, the present coating composition can be a coating layer applied over a basecoat or a coating layer applied over a primer coat, such as the present coating can be a basecoat.

[0090] The substrate can include iron, steel, aluminum, plastic, wood, composite, glass, synthetic material, paper, leather, and / or another coating layer.

[0091] The coating composition can be cured, without limitation, by exposure to ambient conditions, elevated temperature and / or actinic radiation.

[0092] When the coating composition is cured by exposure to elevated temperatures the temperature can be from 40 °C to 240 °C, such as from 45 °C to 210 °C or from 50 °C to 140 °C for from 5 seconds to 168 hours.

[0093] The one component composition of the present disclosure may be an electrodepositable composition, wherein the electrodepositiable composition includes the polyurethane and the hydrophobic component. The emulsifying property of the composition can allow catalyst to be released for cure during or after electrodeposition coating.

[0094] The one component composition can be applied using a method that includes electrophoretically applying the composition in the form of an electrodepositable coating composition to at least a portion of the substrate and curing the coating composition to form an at least partially cured coating on the substrate. According to the present disclosure, the method may include (a) electrophoretically depositing onto at least a portion of the substrate an electrodepositable one component coating composition of the present disclosure and (b)heating the coated substrate to a temperature and for a time sufficient to cure the electrodeposited coating on the substrate. According to the present disclosure, the method may optionally further include (c) applying directly to the at least partially cured electrodeposited coating one or more pigment-containing coating compositions and / or one or more pigment- free coating compositions to form a top coat over at least a portion of the at least partially cured electrodeposited coating, and (d) heating the coated substrate of step (c) to a temperature and for a time sufficient to cure the top coat.

[0095] When the one component composition is a cationic electrodepositable coating composition it may be deposited upon an electrically conductive substrate by placing the composition in contact with an electrically conductive cathode and an electrically conductive anode, with the surface to be coated being the cathode. Following contact with the composition, an adherent film of the coating composition is deposited on the cathode when a sufficient voltage is applied between the electrodes. The conditions under which the electrodeposition is carried out are known in the art. The applied voltage may be varied and can be, for example, as low as one volt to as high as several thousand volts, such as between 50 and 500 volts. The current density may be between 0.5 ampere and 15 amperes per square foot and tends to decrease during electrodeposition indicating the formation of an insulating film.

[0096] Once the cationic electrodepositable coating composition is electrodeposited over at least a portion of the electroconductive substrate, the coated substrate is heated to a temperature and for a time sufficient to at least partially cure the electrodeposited coating on the substrate. As discussed above, the one component electrodepositable coating composition can be cured by heating the coated substrate to a temperature ranging from 120 °C to 230 °C, such as from 135 °C to 200 °C or from 140 °C to 180 °C. The curing time may be dependent upon the curing temperature as well as other variables, for example, the film thickness of the electrodeposited coating, level and type of catalyst present in the composition and the like. For purposes of the present disclosure, all that is necessary is that the time be sufficient to effect cure of the coating on the substrate. As a nonlimiting example, the curing time can range from 10 minutes to 60 minutes, such as 20 to 40 minutes. The thickness of the resultant cured electrodeposited coating may range from 15 to 50 microns.

[0097] According to the present disclosure, when the one component composition is an anionic electrodepositable coating composition it may be deposited upon an electrically conductive substrate by placing the composition in contact with an electrically conductive cathode and an electrically conductive anode, with the surface to be coated being the anode. Following contact with the composition, an adherent film of the coating composition isdeposited on the anode when a sufficient voltage is applied between the electrodes. The conditions under which the electrodeposition is carried out are known in the art. The applied voltage may be varied and can be, for example, as low as one volt to as high as several thousand volts, such as between 50 and 500 volts. The current density may be between 0.5 ampere and 15 amperes per square foot and tends to decrease during electrodeposition indicating the formation of an insulating film.

[0098] Once the anionic electrodepositable coating composition is electrodeposited over at least a portion of the electroconductive substrate, the coated substrate may be heated to a temperature and for a time sufficient to at least partially cure the electrodeposited coating on the substrate. The one component anionic electrodepositable coating composition is capable of curing at a temperature ranging from 90 °C to 230 °C, such as from 135 °C to 200 °C or from 140 °C to 180 °C. The curing time may be dependent upon the curing temperature as well as other variables, for example, film thickness of the electrodeposited coating, level and type of catalyst present in the composition and the like. The curing time may range from 10 to 60 minutes, such as from 20 to 40 minutes. The thickness of the resultant cured electrodeposited coating may range from 15 to 50 microns.

[0099] The coating compositions described herein can have a total resin solids of at least 10 wt. %, such as at least 20 wt. %, or at least 21 wt. %, or at least 22 wt. %, or at least 23 wt. %, or at least 24 wt. %, or at least 25 wt. % and up to 85 wt. %, such as up to 65 wt. %, such as up to 50 wt. %, or up to 45 wt. %, or up to 42 wt. %; or from 10 wt. % to 85 wt. %, such as 20 wt. % to 85 wt. %, such as 20 wt. % to 65 wt. %, such as 20 wt. % to 50 wt. %, or from 21 wt. % to 45 wt. %, or from 22 wt. % to 42 wt. % or from 25 wt. % to 42 wt. % determined as described above.

[0100] The compositions described herein can have a viscosity of from 1 to 5000 cps, such as from 10 to 500 cps, or from 20 to 100 cps measured using a Cone and Plate Viscometer, such as a CAP 2000 viscometer available from Brookfield (AMETEK Brookfield) at 25 °C, 900rpm using spindle number 1.

[0101] The cured layer formed by the methods of the present disclosure may have a solvent resistance of at least 100 MEK double rubs using methods described herein.V. Properties of the Curable composition

[0102] Curable compositions formed using the present disclosure may exhibit increased resistance to solvents as compared to the precursors of the curable composition. The curable composition of the present disclosure may be entirely free of VOC.i. Solvent resistance test

[0103] To test the resistance of a curable composition, a substrate coated with the curable composition may be subjected to a solvent resistance test as described below.

[0104] A solvent resistance test may be performed by placing a test panel on a flat table or other suitable flat, firm surface.

[0105] A disposable wipe (such as a WypAll L30, available from Kimberly-Clark Worldwide, Inc.) is folded to approximately one-inch square dimension in order to test the cured panel for solvent resistance.

[0106] The wipe is saturated with an appropriate solvent, such as methyl ethyl ketone (MEK), for the substrate being tested. The wipe is re-saturated every 25 double rubs.

[0107] The substrate coated with the curable composition is immediately rubbed with the saturated wipe over the test area using a back-and-forth stroke of 2-4 inches.

[0108] The back-and-forth strokes may be continued, counting one “double rub” for each forward and backward motion completed until the bare substrate is exposed in the center of the strip where the rubs are performed or until 100 double rubs are achieved.

[0109] The number of “double rubs” are recorded as the test result. The wipe should be replaced with a new wipe in between each sample tested.

[0110] The curable composition of the present disclosure may have a solvent resistance of at least 70 MEK double rubs, at least 80 MEK double rubs, at least 90 MEK double rubs, or at least 100 MEK double rubs.

[0111] The curable composition of the present disclosure may also have an MEK double rub rating of 7 or greater, such as 8 or greater according to the following scale:

[0112] When the coating compositions described herein include an aqueous dispersion that includes a polyurethane resin and a hydrophobic component, the composition may be evaluated for stability as described below. ii. Stability Test

[0113] To test the stability of aqueous mixtures of a polyurethane resin and a hydrophobic component the mixtures are prepared and visually evaluated for stability according to the following scale:

[0114] Further the stability may be rated at various time intervals after preparation of the mixtures of a polyurethane resin and a hydrophobic component such as initial, 3 hours, 3 days or other time intervals can be employed as required.ASPECTS

[0115] 1. A composition comprising an aqueous dispersion comprising an aqueous medium as a continuous phase and a dispersed phase comprising a polyurethane resin and a hydrophobic component that optionally comprises a hydrophobic crosslinker and / or a hydrophobic catalyst.

[0116] 2. The composition according to aspect 1, wherein the aqueous dispersion is characterized as having no phase separation or reversible phase separation after three hours at ambient conditions.

[0117] 3. The composition according to any preceding aspect, wherein the hydrophobic component comprises a crosslinker.

[0118] 4. The composition according to any preceding aspect, wherein the hydrophobic component comprises a crosslinker comprising epoxy, acrylate, isocyanate and / or aminoplast functional groups.

[0119] 5. The composition according to any preceding aspect, wherein the hydrophobic component comprises a catalyst.

[0120] 6. The composition according to any preceding aspect, wherein the hydrophobic component comprises a catalyst comprising an organometallic and / or an inorganic catalyst.

[0121] 7. The composition according to aspect 6, wherein the organometallic and / or inorganic catalyst comprises a hydrophobic bismuth catalyst, a hydrophobic zinc catalyst, a hydrophobic tin catalyst, a hydrophobic titanium catalyst and / or a hydrophobic zirconium catalyst.

[0122] 8. The composition according to any preceding aspect, wherein the hydrophobic component comprises a catalyst comprising an organic catalyst.

[0123] 9. The composition according to aspect 8, wherein the organic catalyst comprises an amine, quaternary ammonium compound, phosphonium containing compound, and / or quaternary phosphonium group containing compound.

[0124] 10. The composition according to any preceding aspect, wherein the hydrophobic component comprises an additive.

[0125] 11. The composition according to aspect 10, wherein the additive comprises a surfactant, a surface agent, a plasticizer, an antioxidant, a hindered amine light stabilizer, a UV light absorber and / or stabilizer, a flow control agent, a thixotropic agent, a filler, a reactive diluent, a leveling agent, a defoamer and / or a grind vehicle.

[0126] 12. The composition according to any preceding aspect, wherein the aqueous dispersion comprises a film-forming component comprising a binder and a crosslinking agent.

[0127] 13. The composition according to any preceding aspect, wherein the polyurethane resin comprises a water dispersible group.

[0128] 14. The composition according to any preceding aspect, wherein the polyurethane resin comprises water dispersible groups comprising ionic groups and / or nonionic groups.

[0129] 15. The composition according to aspect 13, wherein the polyurethane resin comprises water dispersible groups comprising an acid group, a poly ether group, an hydroxyl group, a thiol group, and / or a non-reactive amine group.

[0130] 16. The composition according to any preceding aspect, wherein the polyurethane resin comprises an acid functional polyurethane having an acid value of from 10 mg KOH / g to150 mg KOH / g , such as from 13 mg KOH / g to 140 mg KOH / g, or from 15 mg KOH / g to 130 mg KOH / g on resin solids according to ASTM D 4662-15.

[0131] 17. The composition according to any preceding aspect, wherein the polyurethane resin comprises a nonionic functional polyurethane comprising polyether and / or polythioether moieties.

[0132] 18. The composition according to any preceding aspect, wherein the polyurethane resin comprises functional groups comprising a thiol group, a hydroxyl group, an alkyl group, a carboxylic acid group, and / or a reactive amine group.

[0133] 19. The composition according to any preceding aspect, wherein the polyurethane resin comprises a nonionic functional polyurethane comprising thiol functional groups.

[0134] 20. The composition according to any preceding aspect, wherein the polyurethane resin comprises an ionic functional polyurethane comprising thiol functional groups.

[0135] 21. The composition according to any preceding aspect, wherein the polyurethane resin has a number average molecular weight of from 400 g / mol to 50,000 g / mol, such as from 500 g / mol to 40,000 g / mol, or from 1000 g / mol to 30,000 g / molas determined by gel permeation chromatography using polystyrene standards.

[0136] 22. The composition according to any preceding aspect, wherein the composition comprises the polyurethane resin at from 1 wt. % to 85 wt. %, such as from 5 wt. % to 80 wt. %, or from 30 wt. % to 70 wt. % of the total resin solids.

[0137] 23. The composition according to any preceding aspect, wherein the hydrophobic component comprises 0.01 to 70 wt. %, such as 1 wt. % to 60 wt. % of total resin solids of the composition.

[0138] 24. The composition according to any preceding aspect having a total resin solids of from 10 wt. % to 85 wt. %, such as 20 wt. % to 85 wt. %, such as 20 wt. % to 65 wt. %, such as 20 wt. % to 50 wt. %, or from 21 wt. % to 45 wt. %, or from 22 wt. % to 42 wt. % or from 25 wt. % to 42 wt. % based on the weight of the composition.

[0139] 25. The composition according to any preceding aspect having a viscosity of from 1 to 5000 cps, such as from 10 to 500 cps, or from 20 to 100 cps using a Cone and Plate Viscometer, such as a CAP 2000 viscometer available from Brookfield (AMETEK Brookfield) at 25 °C, 900 rpm using spindle number 1.

[0140] 26. The composition according to any preceding aspect, wherein the composition is a coating composition.

[0141] 27. The composition according to any preceding aspect comprising multiple components, wherein one component comprises the polyurethane and a different component comprises the hydrophobic component.

[0142] 28. The composition according to any preceding aspect comprising multiple components, wherein one component comprises the polyurethane and the hydrophobic material and another component comprises a film-forming component.

[0143] 29. The composition according to any preceding aspect wherein the polyurethane is part of a film-forming composition and reacts with other components in the composition when applied to a substrate and is cured.

[0144] 30. The composition according to any preceding aspect wherein the composition is applied to a substrate and is cured.

[0145] 31. The composition according to any of aspects 1 through 11, wherein the polyurethane does not react with other components in the composition.

[0146] 32. A method of coating a substrate comprising applying the composition of any one of aspects 1 through 31 over at least a part of a substrate using spray coating, roller coating, coil coating, dip coating, precision coating, draw down coating, electrodeposition coating or spin coating techniques and curing the composition to form a cured layer on the substrate.

[0147] 33. The method according to aspect 32, wherein the composition is cured at a temperature of from 10 °C to 240 °C, such as from 40 °C to 240 °C, or from 45 °C to 210 °C or from 50 °C to 140 °C for from 5 seconds to 168 hours, such as from 10 minutes to 60 minutes, or from 20 to 40 minutes.

[0148] 34. The method according to either of aspects 32 or 33, wherein prior to curing the applied composition, it is flashed at a temperature of from 10 °C to 40 °C for from 0 to 60 minutes.

[0149] 35. The method according to any of aspect 32 through 34, wherein the cured layer has a solvent resistance of at least 70 MEK double rubs, such as at least 80 MEK double rubs, or at least 90 MEK double rubs, or at least 100 MEK double rubs.

[0150] 36. The method according to any of aspect 32 through 35, wherein the cured layer has a dry film thickness of from 0.5 pm to 250 pm, such as from 15 pm to 50 pm measured according to ASTM D7091-21.

[0151] 37. The method according to any of aspect 32 through 36, wherein the composition is a primer, a basecoat, a topcoat, such as a clearcoat, a direct gloss topcoat or monocoat.

[0152] 38. A substrate coated according to the method according to any of aspects 32 through 37.EXAMPLES

[0153] Aspects of the present disclosure are further illustrated by reference to the following examples. It will be apparent to those skilled in the art that many modifications, both to materials, and methods, may be practiced without departing from the scope of the disclosure.THIOL EQUIVALENT WEIGHT

[0154] As used herein, “thiol equivalent weight” was determined in the following examples as follows. A sample (0.2-0.6 g) of the thiol terminated polyurethane was dissolved in 1 ml pyridine and 30 ml of a 1:1 solution by weight of methyl ethyl ketone and toluene. The solution was titrated via colorimetric analysis with 0.1 N iodine solution until a slight yellow color persisted in the solution. Thiol solid equivalent weight was calculated using the following equation. weight of sample (g) * 1000—;. — - — * % solids ml of titrant * 0.1 N iodine

[0155] The reported thiol equivalent weights are the average of triplicate measurements.

[0156] Acid value was determined using a Metrohm 798 MPT Titrino automatic titrator, manufactured by Metrohm AG, according to ASTM D4662-15. The value was then divided by the content of total solids to result in acid value on solids.

[0157] NCO equivalent weight (in grams per equivalent; g / eq) was determined using ASTM D2572-19 (Standard Methods of Isocyanate Groups in Urethane Materials or Prepolymers) revised as follows: A dibutylamine solution of 78 g dibutylamine (available from Sigma Aldrich) in 4 liters of N-methyl-2-pyrrolidone (available from Fisher Scientific) was prepared in advance of sample testing. A sample having a weight between 1 and 2 grams was weighed accurately into a flask. The sample was reacted with 33 ml of the dibutylamine to form a substituted urea. The excess dibutylamine was then back-titrated with a solution of 0.2N hydrochloric acid in isopropyl alcohol (solution available from Fisher Scientific - Ricca). The amount of hydrochloric acid used to back-titrate the excess dibutylamine was used to calculate NCO equivalent weight of the original sample.Example 1 : Formation of a nonionic polyurethane dispersion- thiol functional

[0158] A polyurethane resin was prepared according to the formulation of Table 1. To a four necked reaction flask outfitted with a stirrer, gas inlet, thermometer and condenser was addedthe contents of Charge 1. After the exotherm subsided, the temperature was raised to 80 °C and held for 2 hours. Charge 2 was added followed by Charge 3. The reaction was allowed to exotherm. Once the exotherm subsided the reaction was held at 80 °C until the NCO was undetectable as measured by Fourier Transform Infrared (FTIR) Spectroscopy. The solventborne resin had a measured solids content of 80.5 wt. % and a measured thiol equivalent weight of 441 g / mol iodine on solids. An aqueous dispersion was produced by dispersing 200 grams of material into Charge 4 resulting in a dispersion with a theoretical solids of 40 wt. %.Table 1: Polyurethane Dispersion PUD-11Methoxypolyethylene Glycol 350 available from Dow (Midland, MI, USA)2Aliphatic polyisocyanate resin based on hexamethylene diisocyanate available from Covestro (Pittsburgh, PA, USA)3Dipropylene glycol dimethyl ether available from Dow (Midland, MI, USA)Example 2: Formation of a polyurethane dispersion- thiol functional

[0159] Polyurethane resin was prepared according to the formulation of Table 2.To a four necked reaction flask outfitted with a stirrer, gas inlet, thermometer and condenser was added the contents of Charge 1. After the exotherm subsided, the temperature was raised to 80 °C and held until NCO equivalent weight was above 408 g / eq. The reaction was cooled to 60 °C. Charge 2 was added. The reaction was allowed to exotherm. Once the exotherm subsided the reaction was held at 70 °C for 1.5 hours. The NCO equivalent weight was measured (theory 485 g / eq measured 556 g / eq). Charge 3 was added. The reaction was held at 80 °C until NCO was undetectable as measured by Fourier Transform Infrared (FTIR) Spectroscopy. 498g of the mixture was then dispersed into a mixture of Charge 4 and Charge 5. The dispersion had a measured solid material content of 32.2%, a measured thiol equivalentweight of 539 g / mol iodine on solids and a measured acid value of 9.2 mg KOH / g on resin solids.1Methoxypolyethylene Glycol 350 available from Dow (Midland, MI, USA)2Aliphatic polyisocyanate resin based on hexamethylene diisocyanate available from Covestro (Pittsburgh, PA, USA)3Dipropylene glycol dimethyl ether available from Dow (Midland, MI, USA)Example 3: Formation of a nonionic polyurethane dispersion- thiol functional

[0160] A polyurethane resin was prepared according to the formulation of Table 3.To a four necked reaction flask outfitted with a stirrer, gas inlet, thermometer and condenser was added the contents of Charge 1. After the exotherm subsided, the temperature was raised to 80 °C and held until NCO equivalent weight was above 408 g / eq. The reaction was cooled to 60 °C. Charge 2 was added. The reaction was allowed to exotherm. Once the exotherm subsided the reaction was held at 70 °C for 4.5 hours. The NCO equivalent weight was measured (theory 485 g / eq measured 533 g / eq). Charge 3 was added. The reaction was held at 80 °C until NCO was undetectable as measured by Fourier Transform Infrared (FTIR) Spectroscopy. 498 g of the mixture was then dispersed into a mixture of Charge 4 and Charge 5. The dispersion had a measured solid material of 36.0%, a thiol equivalent weight of 483 g / mol iodine on solids and a measured acid value of 9.8 mg KOH / g on resin solids.1Methoxypolyethylene Glycol 350 available from Dow (Midland, MI, USA)2Aliphatic polyisocyanate resin based on hexamethylene diisocyanate available from Covestro (Pittsburgh, PA, USA)3Dipropylene glycol dimethyl ether available from Dow (Midland, MI, USA)Example 4: Formation of a nonionic polyurethane dispersion- hydroxyl functional

[0161] A polyurethane resin was prepared according to the formulation of Table 4. To a four necked reaction flask outfitted with a stirrer, gas inlet, thermometer and condenser was added the contents of Charge 1. After the exotherm subsided, the temperature was raised to 80 °C and held for 3 hours. The NCO equivalent weight was measured (theory 572 g / eq measured 573 g / eq). The reaction was cooled to 60 °C. Charge 2 was added. The reaction was held at 80 °C until NCO was undetectable as measured by Fourier Transform Infrared (FTIR) Spectroscopy. 492g of the mixture was then dispersed into Charge 3. The dispersion had a measured solid material content of 45.7%.1Methoxypolyethylene Glycol 350 available from Dow (Midland, MI, USA)2Aliphatic polyisocyanate resin based on hexamethylene diisocyanate available from Covestro (Pittsburgh, PA, USA)3Dipropylene glycol dimethyl ether available from Dow (Midland, MI, USA)Example 5: Formation of a nonionic alkyl polyurethane dispersion

[0162] A polyurethane was prepared according to the formulation of Table 5. To a four necked reaction flask outfitted with a stirrer, gas inlet, thermometer and condenser was added the contents of Charge 1. After the exotherm subsided, the temperature was raised to 80 °C and held for 3 hours. The NCO equivalent weight was measured (theory 555 g / eq measured 603 g / eq). The reaction was cooled to 65 °C. Charge 2 was added. The reaction was held at 80 °C until NCO was undetectable as measured by Fourier Transform Infrared (FTIR) Spectroscopy. 363g of the mixture was then dispersed into Charge 3. The dispersion had a measured solid material content of 50.2%.1Methoxypolyethylene Glycol 350 available from Dow (Midland, MI, USA)2Aliphatic polyisocyanate resin based on hexamethylene diisocyanate available from Covestro (Pittsburgh, PA, USA)3Dipropylene glycol dimethyl ether available from Dow (Midland, MI, USA)Example 6: Formation of a polyurethane dispersion-acid functional

[0163] A polyurethane was prepared according to the formulation of Table 6. To a four necked reaction flask outfitted with a stirrer, gas inlet, thermometer and condenser was added the contents of Charge 1. After the exotherm subsided, the temperature was raised to 75 °C and held for 5 hours. The NCO equivalent weight was measured (1312 g / eq, theory 1290 g / eq). The reaction was cooled to 65 °C. Charge 2 was added followed by Charge 3. The reaction was held at 75 °C until the NCO was undetectable as measured by Fourier Transform Infrared (FTIR) Spectroscopy. An aqueous dispersion was produced by adding Charge 4 and Charge 5. Charge 6 was added, and the reaction was allowed to mix at room temperature for 30 minutes. The final dispersion had a measured solids content of 35.3% and a theoretical acid value of 101 mg KOH / g on resin solids.Table 6: Polyurethane Dispersion PUD-64Available from BASF.3Dipropylene glycol dimethyl ether available from Dow (Midland, MI, USA)Example 7 : Formation of a polyurethane dispersion-thiol functional

[0164] A polyurethane was prepared according to the formulation of Table 7. To a four necked reaction flask outfitted with a stirrer, gas inlet, thermometer and condenser was added the contents of Charge 1. After the exotherm subsided, the temperature was raised to 80 °C and held until NCO theory (539 g / eq) was reached. The reaction was cooled to 60 °C and Charge2 was added. The reaction was allowed to exotherm. Once the exotherm subsided the reaction was held at 70 °C for 90 minutes and NCO was measured 1933 g / eq (theory 1167 g / eq). Charge3 was added and the reaction was held at 70 °C until the NCO was undetectable as measured by Fourier Transform Infrared (FTIR) Spectroscopy. An aqueous dispersion was produced byadding Charge 4 and Charge 5. The final dispersion had a measured solids content of 36.0% and a measured thiol equivalent weight of 1404 g / mol iodine on resin solids and a measured acid value of 13.7 mg KOH / g on resin solids.1Methoxypolyethylene Glycol 350 available from Dow (Midland, MI, USA)2Aliphatic polyisocyanate resin based on hexamethylene diisocyanate available from Covestro (Pittsburgh, PA, USA)3Dipropylene glycol dimethyl ether available from Dow (Midland, MI, USA)Example 8: Formation of solventborne aminated epoxy resin

[0165] Epoxy-1 was prepared according to the formulation of Table 8. Materials 1-5 were charged to a 4-neck round bottom flask equipped with overhead stirrer, reflux condenser, thermocouple, and nitrogen inlet. The mixture was heated to 130 °C and allowed to exotherm, then adjusted to 145 °C and held at this temperature for 2 hr. The mixture was then cooled to 105 °C while charging Materials 6-7 sequentially. At 105 °C, Materials 8 and 9 were added rapidly in sequence, and the mixture was allowed to exotherm. The temperature was then adjusted to 125 °C and held for 1 hr. Material 10 was charged while cooling to afford the aminated epoxy resin solution.Table 8: Solventborne aminated epoxy resin Epoxy 15Average epoxy equivalent weight 188 g / eq, available as Epikote 880 from Westlake Chemical. 6Available as Macol 98 B from BASF.’Reaction product of polymeric 4,4’ -methylenediphenyl diisocyanate, available as Mondur MR from Covestro, ethylene glycol butyl ether, and diethylene glycol butyl ether; diluted to 96.3% solids in MIBK. On an equivalent basis, 80% of NCO equivalent reacted with ethylene glycol butyl ether and 20% of NCO equivalent reacted with diethylene glycol butyl ether.8Reaction product of diethylenetriamine and MIBK, -73% solids in MIBK.’Available as Dowanol PM from Dow Chemical Co.Example 9- Formulation of hydrophobic catalyst with waterborne polyurethane dispersion

[0166] Examples A-C were prepared according to Table 9. Mixture 1 was made by combining 9.5 g PUD-5 (Example 5) and 0.5 g dibutyltin dilaurate and mixing by hand until a homogeneous dispersion was observed. Ex. A-C were made by mixing Bayhydrol A2470, followed by Bayhydur 302 (both available from Covestro AG), followed by deionized water and then either Mixture 1 or dibutyltin dilaurate where indicated. The formulas were drawn down using a 6 mil gap square applicator on to 4” x 12” steel substrate which was precoated with an ED7100 electrocoat primer (available from ACT Test Panels LLC, Hillsdale, MI). The films were flashed at ambient conditions for 10 minutes before being baked in a 60 °C oven for 30 minutes. Each coated panel was tested for solvent resistance 1 hour after removal from the oven.Table 9: Incorporation of dibutyltin dilaurate (amounts in g)l0Aqueous hydroxyfunctional polyacrylic dispersion available from Covestro AG "Solvent-free, water-dispersible polyisocyanate available from Covestro AG

[0167] As can be seen in Table 9 above, the inventive Ex. C exhibited the highest MEK DR rating indicating the greatest extent of cure was achieved as compared to no catalyst (Ex. A) or free catalyst (Ex. B).Example 10- Formulation of hydrophobic catalyst with waterborne polyurethane dispersion

[0168] Catalyst mixtures were prepared according to table 10. Materials were added by combining components in a 20 mL vial. Materials were mixed until a homogeneous solution or emulsion was obtained. Formulations were evaluated for initial appearance, then rechecked after 3 hours and 3 days (Table 11) according to the Stability Test described above under ambient conditions.Table 10: Formulation of hydrophobic catalyst with waterborne polyurethane dispersions"Available from Millipore Sigma, average Bi content 20.5 wt. %.' Produced according to procedure for Epoxy 1 for Materials 1-9 in Table 8, followed by dispersion into a solution of 621 g of deionized water and 21.1 g of sulfamic acid, with additional dilution by 476 g of deionized water. Volatile solvents were then removed by vacuum distillation, and deionized water was added to achieve a nonvolatile content of 42 wt. %.Table 11: Appearance of hydrophobic catalyst with waterborne polyurethane dispersions14Appearance definitions: Emulsion- finely dispersed particles to appear to be suspended; precipitate- visible solids not dispersed that fall to bottom of container; mixture=dispersed particles that are larger in size than “emulsion” and may slowly settle15Stability definitions as in Stability Test table

[0169] Examples D-F were prepared according to Table 12. Mixtures were prepared by combining components in a 20 mL vial. Materials were mixed until a homogeneous solution was obtained. Cure testing was carried out by the following procedure: The Epoxy Formulation solution was applied to a cold-rolled steel panel pretreated with C700 zinc phosphate, purchased from ACT Test Panels LLC, using a drawdown bar with 1 mil gap. Panels were flashed 5-10 minutes at ambient conditions and subsequently baked in a 175 °C oven for 30 min. Continuous films were obtained for all samples. Cure was evaluated by solvent resistance as determined using the MEK double rub test described above as shown in Table 13. Retention of performance was tested in two ways: 1) Epoxy Formulations were reapplied and cured after 4 day aging at ambient temperature, and 2) Epoxy Formulations were remade using 5 day ambient-aged Catalyst Mixtures, followed by application and cure as described.Table 12: Examples of catalyst mixtures with epoxy resin and curability testing by drawdownTable 13: Appearance and solvent resistance of catalyst mixtures with epoxy resin and curability testing by drawdown

[0170] The Catalyst Mixtures and Epoxy Formulations were able to be reapplied with full retention of cure performance after multiple days as shown by an MEK DR of >100 for each inventive example. Formulation using Catalyst Mixture 4 were not carried because of the lack of stability of the catalyst (hydrophobic component) without polyurethane.Example 11- Incorporation of dibutyltin dilaurate

[0171] Examples G-I were prepared according to Table 14. The formulations were prepared in a 20 mL scintillation vial. Coatings were formulated using a 1 : 1 ratio of thiol equivalents to reactive equivalents (Acrylate, epoxy, or isocyanate). Order of addition for mixing is listed below in the formulation information. Each formulation was drawn down using a 8 mil square bar over an ED7100 electrocoated steel panel available from ACT Test Panel Technologies (273 Industrial Dr., Hillsdale, MI 49242). The panels were allowed to flash at ambient conditions for 10 minutes then placed in a 60 °C oven for 45 min for cure. Panels were allowed to sit for 24 hrs. and then evaluated for MEK resistance.Table 14: Preparation and results of Ex. G-I (amounts in g)16Ethoxylated 3 Trimethylolpropane Triacrylate available from Sartomer (King of Prussia, PA)17Sorbitol polyglycidyl ether tetrafunctional epoxy available from Nagase Specialty Materials (Itasca, IL)18Polycthcr modified Siloxane available from B YK (Wallingford, CT)19Aliphatic polyisocyanate (hexamethylene diisocyanate uretdione) available from Covestro (Pittsburgh, PA)2010wt% solution of diazobicycloctene (DABCO) in water

[0172] As can be seen in Table 14 a variety of curing chemistries are demonstrated, including acrylate, epoxy, and isocyanate, each cured with the thiol functional group of PUD-1. Examples G, H, and I all demonstrate 100 MEK DR and an MEK DR rating or 7 or greater. Further, these examples show a beneficial solids / viscosity relationship, having useful viscosity at relatively high solids.

[0173] Whereas particular examples of the compositions and methods according to this disclosure have been described above for purposes of illustration, it will be evident to those skilled in the art that numerous variations of the details of the present disclosure may be made without departing from the description as defined in the appended claims.

Claims

CLAIMSWhat is claimed is:

1. A composition comprising an aqueous dispersion comprising an aqueous medium as a continuous phase and a dispersed phase comprising a polyurethane resin and a hydrophobic component that optionally comprises a hydrophobic crosslinker and / or a hydrophobic catalyst.

2. The composition according to claim 1, wherein the aqueous dispersion is characterized as having no phase separation or reversible phase separation after three hours.

3. The composition according to any preceding claim, wherein the composition is curable.

4. The composition according to any preceding claim, wherein the hydrophobic component comprises a crosslinker comprising epoxy, acrylate, isocyanate and / or aminoplast functional groups; and / or a catalyst, such as an organic catalyst, an organometallic and / or an inorganic catalyst; and / or an additive.

5. The composition according to any preceding claim, wherein the aqueous dispersion comprises a film-forming component comprising a binder and a crosslinking agent.

6. The composition according to any preceding claim, wherein the polyurethane resin comprises a water dispersible group comprising an ionic group and / or a nonionic group.

7. The composition according to any preceding claim, wherein the polyurethane resin comprises an acid functional polyurethane having an acid value of from 1 mg KOH / g to 150 mg KOH / g on resin solids according to ASTM D 4662-15; and / or comprises a nonionic functional polyurethane comprising polyether and / or poly thioether moieties; and / or comprises functional groups comprising a thiol group, a hydroxyl group, an alkyl group, a carboxylic acid group, and / or a reactive amine group.

8. The composition according to any preceding claim, wherein the polyurethane resin has a number average molecular weight of from 400 g / mol to 50,000 g / mol as determined by gel permeation chromatography using polystyrene standards.

9. The composition according to any preceding claim, wherein the composition comprises the polyurethane resin at from 1 wt. % to 85 wt. % based on total resin solids.

10. The composition according to any preceding claim, wherein the hydrophobic component comprises 0.01 to 70 wt. % of total resin solids based on the total resin solids.

11. The composition according to any preceding claim, wherein the composition is a coating composition.

12. The composition according to any preceding claim, wherein the aqueous dispersion is characterized as having no phase separation after three hours at ambient conditions.

13. The composition according to any preceding claim comprising multiple components, wherein one component comprises the polyurethane and a different component comprises the hydrophobic component.

14. The composition according to any preceding claim comprising multiple components, wherein one component comprises the polyurethane and the hydrophobic material and another component comprises a film-forming component.

15. A method of coating a substrate comprising applying the composition of any one of claims 1 through 14 over at least a part of a substrate using spray coating, roller coating, coil coating, dip coating, precision coating, draw down coating, electrodeposition coating or spin coating techniques and curing the composition to form a cured layer on the substrate.

16. The method according to claim 15, wherein the curable composition is cured at a temperature of from 10 °C to 210 °C, for from 5 seconds to 168 hours and is optionally flashed at a temperature of from 10 °C to 40 °C for from 0 to 60 minutes prior to curing.

17. The method according to either of claim 15 or 16, wherein the cured layer has a solvent resistance of at least 100 MEK double rubs.

18. The method according to any of claim 15 through 17, wherein the cured layer has a dry film thickness of from 0.5 pm to 250 pm measured according to ASTM D7091-21.

19. The method according to any of claim 15 through 18, wherein the composition is a primer, a basecoat, a topcoat, such as a clearcoat, a direct gloss topcoat or monocoat.

20. A substrate coated according to the method according to any of claims 15 through 19.