Electrodepositable coating compositions comprising a bismuth catalyst

Abstract

The present disclosure is directed to electrodepositable coating compositions comprising a cationic salt group-containing film-forming polymer; a blocked polyisocyanate curing agent; a bismuth catalyst; and an acid scavenger, metal oxide and / or metal acetate is disclosed. Also disclosed are pigment pastes, methods for coating substrates, and substrates coated thereby.

Description

ELECTRODEPOSITABLE COATING COMPOSITIONSCOMPRISING A BISMUTH CATALYSTCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims priority to U.S. Provisional Application Serial No. 63 / 556,320, filed February 21, 2024 and U.S. Provisional Application Serial No. 63 / 556,644, filed February 22, 2024, both entitled “Electrodepo sitable Coating Compositions”, which are incorporated herein in their entirety.FIELD

[0002] The present disclosure is directed towards electrodepositable coating compositions comprising a film-forming polymer, a blocked polyisocyanate, a bismuth catalyst, and an acid scavenger, a metal oxide and / or a metal acetate. Pigment pastes, methods of using the coating compositions to coat substrates, and substrates coated thereby are disclosed.BACKGROUND

[0003] Electrodeposition as a coating application method involves the deposition of a film-forming composition onto a conductive substrate under the influence of an applied electrical potential. Electrodeposition has gained popularity in the coatings industry because it provides higher paint utilization, outstanding corrosion resistance, and low environmental contamination as compared with non-electrophoretic coating methods.SUMMARYDisclosed herein are electrodepositable coating compositions comprising a cationic salt group-containing film-forming polymer comprising active hydrogen functional groups; a blocked polyisocyanate curing agent; a bismuth catalyst; and an acid scavenger, metal oxide and / or metal acetate; with the provisos that: the electrodepositable coating composition is substantially free, essentially free, or completely free of a dispersing acid comprising an oxyacid of phosphorus, the P:B of the composition is 0.2: 1 or greater, and when the acid scavenger comprises hydrotalcite, the hydrotalcite is substantially free of of divalent metals other than magnesium and / or the hydrotalcite has more than one magnesium atom per molecule of hydrotalcite.

[0004] The present disclosure is also directed to pigment pastes for an electrodepo sitable coating composition comprising a grind resin; and pigment component comprising a plate-like pigment and an acid scavenger, metal oxide, and / or metal acetate, wherein the plate-like pigment is present in an amount of at least 50% by weight, based on the total weight of pigment in the pigment component, and the metal oxide does not comprise yttrium oxide.

[0005] The present disclosure is also directed to pigment pastes comprising a cationic salt group-containing resin; a bismuth catalyst; and a pigment comprising an acid scavenger, metal oxide, and / or metal acetate and when the acid scavenger comprises hydrotalcite, the hydrotalcite is substantially free of divalent metals other than magnesium, and / or the hydrotalcite has more than one magnesium atom per molecule of hydrotalcite.

[0006] The present disclosure also provides a method for using the electrodepo sitable coating compositions to coat a substrate by electrodeposition of the coating composition onto at least a portion of the substrate. Substrates coated thereby are also within the present scope.DETAILED DESCRIPTION

[0007] The present disclosure provides electrodepo sitable coating compositions comprising a cationic salt group-containing film-forming polymer comprising active hydrogen functional groups; a blocked polyisocyanate curing agent; a bismuth catalyst; and an acid scavenger, metal oxide, and / or metal acetate. An “electrodepositable coating composition” will be understood as referring to a composition that is capable of being deposited onto an electrically conductive substrate under the influence of an electrical potential applied between two electrodes immersed in the electrodepositable coating composition, where one of the electrodes is the substrate to be coated. The present coating may be described herein in terms of a coating composition, which will be understood as referring to an uncured or unhardened mixture of coating components. The coating composition can be deposited and cured to form a coating or coating layer, which terms may be used interchangeably herein.

[0008] The electrodepositable coating compositions of the present disclosure comprise a film-forming component comprising a cationic salt group-containing film-forming polymer and a blocked polyisocyanate curing agent; the polymer and curing agent are sometimes collectively referred to herein as an electrodepositable binder. A cationic salt group-containing film-forming polymer refers to film-forming polymers that include at least partially neutralized cationic salt groups, such as amine, sulfonium and / or ammonium salt groups, that impart a positive charge.The cationic salt group-containing film-forming polymer comprises active hydrogen functional groups, which refers to those functional groups that are reactive with isocyanates, and include, for example, hydroxyl groups, primary or secondary amine groups, carbamates, and thiol groups. As used herein, the term “film-forming polymer” may be used interchangeably with “polymer” or “resin”, and refers to one or more polymers, such as homo polymers and / or copolymers, as well as prepolymers, oligomers, and monomers, that, upon hardening and / or curing, such as by reaction with a crosslinker, can form a continuous film on a surface. The terms “crosslinker”, “crosslinking agent”, or “curing agent”, may be used interchangeably herein. “Cure”, “harden” and like terms may also be used inter-changeably herein and refer to the ability of at least a portion of the polymerizable and / or crosslinkable components to undergo a reaction.

[0009] The film-forming polymer may be organic or inorganic. An “organic” filmforming polymer is one with a skeletal structure that includes a carbon atom in the backbone, while an “inorganic” film-forming polymer refers to one with a skeletal structure that does not include carbon atoms in the backbone; a suitable example is one that comprises silicone-based materials. It will be understood that the electrodepo sitable binder may also comprise a mixture of organic and inorganic film-forming polymers and / or curing agent materials.

[0010] Polymers that are suitable for use as the cationic salt group-containing filmforming polymer of the electrodepo sitable coating composition include, but are not limited to, alkyd polymers, acrylics, polyepoxides, polyamides, polyurethanes, polyureas, polyethers, and polyesters, as well as adducts, derivatives and combinations thereof. For example, the cationic salt group-containing film-forming polymer may comprise a reaction product of reactants comprising (a) a polyepoxide; (b) a di-functional chain extender; and (c) a mono-functional reactant, such as the polymers described in IntT App. No. PCT / US22 / 73356, at paragraphs

[0023] to

[0038] , the cited portion of which is incorporated herein by reference. Particularly suitable are di-epoxides, such as the diglycidyl ethers of bisphenol, such as bisphenol A (BADGE) and bisphenol F (BFDGE).

[0011] The cationic salt group-containing film-forming polymer may be made cationic and water dispersible by at least partial neutralization with an acid such as formic acid, acetic acid, methanesulfonic acid, lactic acid, phosphoric acid and / or sulfamic acid. The extent of neutralization of the cationic salt group-containing film-forming polymer may vary with the particular polymer used. However, sufficient acid should be used to neutralize the cationic saltgroup-containing film-forming polymer such that the cationic salt group-containing film-forming polymer may be dispersed in an aqueous dispersing medium. For example, the amount of acid used may provide at least 20% of all the total theoretical neutralization. Alternatively, the amount of acid used may provide in excess of 100% of all of the total theoretical neutralization. The total amount of acid used to neutralize the cationic salt group-containing film-forming polymer may range from any combination of values, for example, such as at 20% or more, to greater than 100%, inclusive of the recited values. For example, the total amount of acid used to neutralize the active hydrogen-containing, cationic salt group-containing film-forming polymer may be at least 20%, 35%, 50%, 60%, 80%, or 100% or greater, based on the total amines in the cationic salt group-containing film-forming polymer.

[0012] Suitable inorganic electrodepositable film-forming polymers include silicone- based film-forming polymers, such as those described in IntT Pub. No. WO 2021 / 138384 Al, at paragraphs

[0007] through

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

[0013] The cationic salt group-containing film-forming polymer may be present in the electrodepositable coating composition in an amount of at least 40% by weight, such as at least 50% by weight, such as at least 55% by weight, such as at least 60% by weight, based on the total weight of the resin solids of the electrodepositable coating composition. The cationic salt group-containing film-forming polymer may be present in the electrodepositable coating composition in an amount of no more than 90% by weight, such as no more than 80% by weight, such as no more than 75% by weight, based on the total weight of the resin solids of the electrodepositable coating composition. The cationic salt group-containing film-forming polymer may be present in the electrodepositable coating composition, in an amount of 40% to 90% by weight, such as 40% to 80% by weight, such as 40% to 75% by weight, such as 50% to90% by weight, such as 50% to 80% by weight, such as 50% to 75% by weight, such as 55% to90% by weight, such as 55% to 80% by weight, such as 55% to 75% by weight, such as 60% to90% by weight, such as 60% to 80% by weight, such as 60% to 75% by weight, based on the total weight of the resin solids of the electrodepositable coating composition.

[0014] As used herein, the “resin solids” include the cationic salt group-containing filmforming polymer, the curing agent (including any volatilizable blocking agents thereof), and any additional water-dispersible component(s) present in the electrodepositable coating composition; the pigment component(s) are not considered resin solids.

[0015] As noted above, the electrodepositable coating composition of the present disclosure further comprises a blocked polyisocyanate curing agent. Other suitable curing agents could optionally be included, such as aminoplast resins and / or phenoplast resins, such as phenolformaldehyde condensates including allyl ether and / or derivatives thereof.

[0016] As used herein, a “blocked polyisocyanate” means a polyisocyanate wherein at least a portion of the isocyanato groups is blocked by a blocking group introduced by the reaction of a free isocyanato group of the polyisocyanate with a blocking agent. By “blocked” is meant that the isocyanato groups have been reacted with a blocking agent such that the resultant blocked isocyanate group is stable to active hydrogens at ambient temperature, e.g., room temperature (23 °C). The reaction may be reversed under suitable conditions, such as at elevated temperatures, such as, e.g., 90°C to 200°C, such that the previously blocked isocyanato groups on the polyisocyanate curing agent are unblocked and available to react with the reactive groups, such as the active hydrogen groups, of the cationic salt group-containing film- forming polymer to effectuate cure of the coating composition to form a coating layer.

[0017] Blocking agents that are disassociated from the blocked polyisocyanate curing agent during cure may be removed from the coating by volatilization. Alternatively, at least a portion of the blocking agent may remain in the coating following cure.

[0018] Suitable blocked polyisocyanate curing agents, and amounts thereof, including suitable polyisocyanates, and blocking components such as blocking groups and / or blocking agents, such as but not limited to 1,2 polyols, are provided in Int’l Pub. No. WO 2021 / 138583 Al, at paragraphs

[0022] to

[0035] , the cited portion of which is incorporated herein by reference. The 1,2-alkane diol may comprise ethylene glycol, propylene glycol, 1,2-butane diol, 1,2-pentane diol, 1,2-hexane diol, 1,2-heptanediol, 1,2-octanediol, glycerol esters or ethers having a 1,2-dihydroxyl-functionality, and the like, and may include combinations thereof.

[0019] The 1,2-polyol may comprise at least 30% of the blocking groups, such as at least 35%, such as at least 40%, such as at least 45%, such as at least 50%, such as at least 55%, such as at least 60%, such as at least 65%, such as at least 70%, such as at least 75%, such as at least 80%, such as at least 85%, such as at least 90%, such as at least 95%, such as at least 99%, such as 100%, based upon the total number of blocking groups. The 1,2-polyol may comprise no more than 100% of the blocking groups of the blocked polyisocyanate curing agent, such as no more than 99%, such as no more than 95%, such as no more than 90%, such as no more than85%, such as no more than 80%, such as no more than 75%, such as no more than 70%, such as no more than 65%, such as no more than 60%, such as no more than 55%, such as no more than 50%, such as no more than 45%, such as no more than 40%, such as no more than 35%, such as no more than 30%, based upon the total number of blocking groups. The 1,2-polyol may comprise 30% to 100% of the blocking groups of the blocked polyisocyanate curing agent, such as 35% to 100%, such as 40% to 100%, such as 45% to 100%, such as 50% to 100%, such as 55% to 100%, such as 60% to 100%, 65% to 100%, such as 70% to 100%, such as 75% to 100%, such as 80% to 100%, 85% to 100%, such as 90% to 100%, such as 95% to 100%, such as 30% to 95%, such as 35% to 95%, such as 40% to 95%, such as 45% to 95%, such as 50% to 95%, such as 55% to 95%, such as 60% to 95%, 65% to 95%, such as 70% to 95%, such as 75% to 95%, such as 80% to 95%, 85% to 95%, such as 90% to 95%, based upon the total number of blocking groups. As used herein, the percentage of blocking groups of the blocked polyisocyanate curing agent with respect to a blocking agent refers to the molar percentage of isocyanato groups blocked by that blocking agent divided by the total number of isocyanato groups actually blocked, i.e., the total number of blocking groups. The percentage of blocking groups may be determined by dividing the total moles of blocking groups blocked with a specific blocking agent by the total moles of blocking groups of the blocked polyisocyanate curing agent and multiplying by 100. It may also be expressed in equivalents of the blocking agent to total equivalents of isocyanato groups from the polyisocyanate, and the percentages and equivalents may be converted and used interchangeably (e.g., 40% of the total blocking groups is the same as 4 / 10 equivalents).

[0020] The blocked polyisocyanate may comprise a blocking group derived from a blocking agent comprising an alpha-hydroxy amide, ester, or thioester as provided in Int’l Pub. No. WO 2018 / 148306 Al, at paragraphs

[0010] to

[0029] , the cited portion of which is incorporated herein by reference. The blocked polyisocyanate may be a fully blocked polyisocyanate wherein essentially 100% of the isocyanato groups of the polyisocyanate are blocked with one or more blocking groups. Optionally, the blocked polyisocyanate curing agent may be an at least partially blocked polyisocyanate, having fewer than 100% of the isocyanato groups blocked, as long as the coating composition remains a stable dispersion. Combinations of blocking agents may be used.

[0021] The blocking agent may also comprise aliphatic, cycloaliphatic, or aromatic alkyl monoalcohols or phenolic compounds, including, for example, lower aliphatic alcohols, such as methanol, ethanol, and n-butanol; cycloaliphatic alcohols, such as cyclohexanol; aromatic-alkyl alcohols, such as phenyl carbinol and methylphenyl carbinol; and phenolic compounds, such as phenol itself and substituted phenols wherein the substituents do not affect coating operations, such as cresol and nitrophenol. Glycol ethers and glycol amines may also be used as blocking agents. Suitable glycol ethers include ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether and propylene glycol methyl ether. Other suitable blocking agents include oximes, such as methyl ethyl ketoxime, acetone oxime and cyclohexanone oxime. Other blocking agents include a 1,3-alkane diol, such as, for example, 1,3-butanediol; a benzylic alcohol, for example, benzyl alcohol; an allylic alcohol, for example, allyl alcohol; caprolactam; a dialkylamine, for example dibutylamine; furfuryl alcohol; other diol, triol, or polyols; and mixtures thereof.

[0022] The at least partially blocked polyisocyanate may be partially blocked with one or more of the blocking groups discussed above, with the remaining isocyanate groups reacted with a compound or polymer, such as described in U.S. Pat. No. 3,947,338, at col. 2, line 65 through col. 5, line 33, the cited portion of which is herein incorporated by reference.

[0023] The blocked polyisocyanate curing agent may comprise a tris(alkoxycarbonylamino)-l,3,5-triazine (TACT), such as tris(methoxycarbonylamino)-, tris(butoxycarbonylamino)-, and tris(2-ethylhexoxycarbonylamino)-l,3,5-triazines, and any combination thereof.

[0024] The curing agent may further comprise an aminoplast or a phenoplast resin. Aminoplast resins are condensation products of an aldehyde with an amino- or amido-group carrying substance. Phenoplast resins are formed by the condensation of an aldehyde and a phenol.

[0025] Commercially available aminoplast resins include those available under the trademark CYMEL from Allnex Belgium SA / NV, such as CYMEL 1130 and 1156, and RESIMENE from INEOS Melamines, such as RESIMENE 750 and 753. Examples of suitable aminoplast resins, and amounts thereof, also include those described in U.S. Pat. No. 3,937,679 at col. 16, line 3 to col. 17, line 47, this portion of which being hereby incorporated by reference, which also includes use of the aminoplast in combination with methylol phenol ethers.

[0026] Suitable aminoplast and phenoplast resins also are described in U.S. Pat. No. 4,812,215 at col.6, line 20 to col. 7, line 12, the cited portion of which being incorporated herein by reference.

[0027] The curing agent may comprise or further comprise an inorganic curing agent, such as the silicone-based curing agents described in Int’l Pub. No. WO 2021 / 138384 Al, at paragraphs

[0030] through

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

[0028] The curing agent, including the blocked polyisocyanate curing agent and any second curing agent if used, may be present in the electrodepo sitable coating composition in an amount of at least 10% by weight, such as at least 20% by weight, such as at least 25% by weight, based on the total weight of the resin solids of the electrodepositable coating composition. The curing agent may be present in the electrodepositable coating composition, in an amount of no more than 60% by weight, such as no more than 50% by weight, such as no more than 45% by weight, such as no more than 40% by weight, based on the total weight of the resin solids of the electrodepositable coating composition. The curing agent may be present in the electrodepositable coating composition, in an amount of 10% to 60% by weight, such as 10% to 50% by weight, such as 10% to 45% by weight, such as 10% to 40% by weight, such as 20% to 60% by weight, such as 20% to 50% by weight, such as 20% to 45% by weight, such as 20% to 40% by weight, such as 25% to 60% by weight, such as 25% to 50% by weight, such as 25% to 45% by weight, such as 25% to 40% by weight, based on the total weight of the resin solids of the electrodepositable coating composition.

[0029] The electrodepositable coating compositions further comprise a bismuth catalyst. As used herein, the term “catalyst” may be used interchangeably with “curing catalyst” and refers to a substance that increases the rate or decreases the activation energy of a chemical reaction without itself undergoing any permanent chemical change. For example, the bismuth catalyst may catalyze transurethanation reactions and specifically catalyze the deblocking of blocked polyisocyanate blocking groups; non-catalytic forms of the metal, such as bismuth metal compounds used as pigments, are not included in “bismuth catalysts” as used herein.

[0030] The bismuth catalyst may comprise a soluble bismuth catalyst. As used herein, a “soluble” or “solubilized” bismuth catalyst is at catalyst wherein at least a portion of the bismuth metal from the bismuth catalyst is dissolved in the aqueous medium of the electrodepositable coating composition, such as, for example, at least 5% by weight of bismuth metal from thebismuth catalyst is dissolved based on the total weight of the bismuth metal from the bismuth catalyst, such as at least 10% by weight, such as at least 20% by weight, such as at least 30% by weight, such as at least 35% by weight, such as at least 40% by weight, such as at least 45% by weight, such as at least 50% by weight. The percentage of solubilized bismuth present in the electrodepositable coating composition may be determined using inductively coupled plasma optical emission spectroscopy (“ICP-OES”) to calculate the total amount of bismuth (i.e., solubilized and non- solubilized) and total amount of solubilized bismuth and calculating the percentage using those measurements. The soluble bismuth catalyst may be at least partially predissolved prior to addition to the electrodepositable coating composition or dissolved in situ in the electrodepositable coating composition.

[0031] The amount of solubilized and non- solubilized bismuth concentrations reported herein were determined using ICP-OES. The total bismuth metal content is the sum of the solubilized and the non- solubilized bismuth metal in the electrodepositable coating composition. The solubilized bismuth metal from the electrodepositable coating composition is determined as follows: 10g of the respective electrocoating composition is weighed into a centrifuge tube and subsequently subjected to centrifugation for 30 minutes at 17,000 rpm. Afterwards, all the supernatant is decanted into a tared tube. Ultrapure water is then added to the decanted supernatant to bring the mass of the tared tube to 10g. An aliquot of 2g of supernatant is then added to a centrifuge tube containing 0.5 mL of an internal standard (1,000 ppm Re standard solution). The resulting mixture is then diluted with ultrapure water to a total sample volume of 50 mL. The sample is then measured with ICP-OES. The total bismuth from the electrodepositable coating composition is determined as follows: 0.5g of the respective electrodepositable coating composition is weighed directly into a microwave digestion vessel. To the vessel is added 10 mL HNO3, 2mL HC1, and 0.5 mL HF. The vessel is then placed in a microwave digester and digested using the following microwave digestion program:

[0032] After the digestion program is complete, the digested solution is quantitatively transferred from the vessel to a graduated cylinder and diluted with 50 mL of ultrapure water. The sample is then measured with ICP-OES.

[0033] The bismuth catalyst may be present in an amount such that the amount of solubilized bismuth metal may be at least 0.005% by weight, based on the total weight of the electrodepositable coating composition, such as at least 0.01% by weight, such as at least 0.04% by weight, such as at least 0.06% by weight, such as at least 0.07% by weight, such as at least 0.08% by weight, such as at least 0.09% by weight, such as at least 0.10% by weight, such as at least 0.11% by weight, such as at least 0.12% by weight, such as at least 0.13% by weight, such as at least 0.14% by weight, or higher.

[0034] The bismuth catalyst may be present in an amount such that the amount of solubilized bismuth metal may be at least 0.05% by weight, at least 0.22% by weight, based on the total weight of the resin solids, such as at least 0.01% by weight, such as at least 0.22% by weight, such as at least 0.30% by weight, such as at least 0.34% by weight, such at least 0.40% by weight, such as at least 0.45% by weight, such as 0.51% by weight, such as at least 0.56% by weight, such as at least 0.62% by weight, such as at least 0.68% by weight, such as at least 0.73% by weight, such as at least 0.80% by weight, or higher.

[0035] The total amount of bismuth metal introduced into the composition from the bismuth catalyst is not limited but may be up to 30,000 ppm or higher. The composition may include at least 10 ppm soluble bismuth metal, such as at least 100 ppm soluble bismuth metal, such as at least 150 ppm soluble bismuth metal, such as at least 200 ppm soluble bismuth metal, such as at least 300 ppm soluble bismuth metal, such as at least 500 ppm soluble bismuth metal, such as at least 1,000 ppm soluble bismuth metal, such as at least 3,000 ppm soluble bismuth metal, such as at least 5,000 ppm soluble bismuth metal, such as at least 10,000 ppm soluble bismuth metal, such as at least 15,000 ppm soluble bismuth metal. The composition may include no more than 20,000 ppm soluble bismuth metal, such as no more than 15,000 ppm soluble bismuth metal, such as no more than 10,000 ppm soluble bismuth metal, such as no more than 5,000 ppm soluble bismuth metal, such as no more than 3,000 ppm soluble bismuth metal, suchas no more than 1,000 ppm soluble bismuth metal, such as no more than 800 ppm soluble bismuth metal, such as no more than 600 ppm soluble bismuth metal, such as no more than 500 ppm, such as no more than 400 ppm. The composition may include 10 to 20,000 ppm soluble bismuth metal, such as 100 to 20,000 ppm soluble bismuth metal, such as 150 to 15,000 ppm soluble bismuth metal, such as 200 to 10,000 ppm soluble bismuth metal, such as 300 to 5,000 ppm soluble bismuth metal, such as 500 to 3,000 ppm soluble bismuth metal, such as 10 to 1,000 ppm soluble bismuth metal, such as 100 to 1,000 ppm soluble bismuth metal, such as 100 to 800 ppm soluble bismuth metal, such as 100 to 600 ppm soluble bismuth metal, such as 100 to 500 ppm soluble bismuth metal, such as 100 to 400 ppm soluble bismuth metal, such as 150 to 1,000 ppm soluble bismuth metal soluble bismuth metal, such as 150 to 800 ppm soluble bismuth metal, such as 150 to 600 ppm soluble bismuth metal, such as 150 to 500 ppm soluble bismuth metal, such as 150 to 400 ppm soluble bismuth metal.

[0036] The bismuth catalyst may comprise a bismuth compound and / or complex.

[0037] The bismuth catalyst may, for example, comprise a colloidal bismuth oxide or bismuth hydroxide, a bismuth compound complex such as, for example, a bismuth chelate complex, or a bismuth salt of an inorganic or organic acid, wherein the term “bismuth salt” includes not only salts comprising bismuth cations and acid anions, but also bismuthoxy salts. Examples of inorganic or organic acids from which the bismuth salts may be derived are hydrochloric acid, nitric acid, sulphuric acid, inorganic or organic sulphonic acids, carboxylic acids, for example, formic acid or acetic acid, amino carboxylic acids and hydroxy carboxylic acids, such as lactic acid or dimethylolpropionic acid.

[0038] Suitable bismuth salts include aliphatic hydroxy carboxy lie acid salts of bismuth, such as lactic acid salts or dimethylolpropionic acid salts of bismuth, for example, bismuth lactate or bismuth dimethylolpropionate; amidosulphonic acid salts of bismuth; hydrocarbylsulphonic acid salts of bismuth, such as alkyl sulphonic acid salts, including methane sulphonic acid salts of bismuth, for example, bismuth methane sulphonate, bismuth ethane sulphonate, as well as combinations thereof. Further examples of bismuth compound or complex catalysts include bismuth oxides, bismuth carboxylates, bismuth subnitrate, bismuth sulfamate, bismuth sulphonate, and combinations thereof.

[0039] The bismuth catalyst may be a bismuth catalyst that is not a bismuth compound having a ligand prepared from a P-diketone. The electrodepositable coating composition may besubstantially free, essentially free, or completely free of a bismuth compound having a ligand prepared from a p-diketone. As used herein, an electrodepo sitable coating composition is “substantially free” of a bismuth compound having a ligand prepared from a P-diketone if such compound is present, if at all, in an amount of less than 0.1% by weight or less than 0.01% by weight, respectively, based on resin solids weight. As used herein, an electrodepositable coating composition is “completely free” of a bismuth compound having a ligand prepared from a P- diketone if such compound is not present, i.e., 0.00% by weight, based on resin solids weight.

[0040] The bismuth catalyst may be present in an amount of at least 0.01% by weight of bismuth metal, such as at least 0.1% by weight, such as at least 0.2% by weight, such as at least 0.5% by weight, such as at least 1.0% by weight, such as 1.0% by weight, based on the total resin solids weight of the composition. The bismuth catalyst may be present in an amount of no more than 3.0% by weight of bismuth metal, such as no more than 1.5% by weight, such as no more than 1.0% by weight, based on the total resin solids weight of the composition. The bismuth catalyst may be present in an amount of 0.01% to 3.0% by weight of bismuth metal, such as 0.1% to 1.5% by weight, such as 0.2% to 1.0% by weight, such as 0.5% to 3.0% by weight, such as 0.5% to 1.5% by weight, such as 0.5% to 1.0% by weight, such as 1.0% to 3.0% by weight, such as 1.0% to 1.5% by weight, based on the total resin solids weight of the composition.

[0041] The electrodepositable coating compositions of the present disclosure may further comprise a co-catalyst in addition to the bismuth catalyst. Suitable curing catalysts that could be used as the co-catalyst include amine-containing compounds; compounds or complexes of metals such as tin, cerium, zinc, and / or titanium; and combinations thereof.

[0042] Suitable amine-containing curing catalysts may comprise any suitable amine- containing curing catalyst, such as, but not limited to, curing catalysts comprising a guanidine, an imidazole, an amidine, and / or derivatives or combinations thereof. Suitable guanidine curing catalysts are provided in U.S. Pat. No. 7,842,762 at col. 1, line 53 to col. 3, line 46, the cited portion of which is incorporated herein by reference. Suitable imidazole curing catalysts are described in U.S. Pub. No. 2022 / 0154014 Al, as paragraphs

[0062] to

[0108] , the cited portion of which is incorporated herein by reference. The amidine curing catalyst may, in a non-limiting example, comprise l,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0043] Suitable zinc-containing catalysts may comprise a metal salt and / or complex of zinc such as, but not limited to, a zinc (II) amidine complex, zinc octoate, zinc naphthenate, zinc tallate, zinc carboxylates having from 8 to 14 carbons in the carboxylate group, zinc acetate, zinc sulfonates, zinc methanesulfonates, or any combination thereof. The zinc (II) amidine complex may contain amidine and carboxylate ligands.

[0044] The curing catalyst may comprise a titanium compound and / or complex such as, for example, Ti(OR1)4, wherein R1is an alkyl or aryl, such as wherein R1is a C3-C20 alkyl, such as wherein R1is n-butyl, such as tetrabutyl titanate.

[0045] The electrodepo sitable coating composition may be substantially free, essentially free, or completely free of catalytic tin. As used herein, “catalytic tin” refers to tin compounds that function as a curing catalyst. An electrodepo sitable coating composition is “substantially free” of catalytic tin if catalytic tin is present in an amount of less than 0.1% by weight, based on the total weight of the electrodepositable coating composition, “essentially free” of catalytic tin if catalytic tin is present in an amount of less than 0.01% by weight, based on the total weight of the electrodepositable coating composition, and “completely free” of catalytic tin if catalytic tin is present in an amount of less than 0.001%, based on the total weight of the electrodepositable coating composition.

[0046] The electrodepositable coating composition may be substantially free, essentially free, or completely free of bismuth subnitrate, bismuth silicate, and / or bismuth titanate. An electrodepositable coating composition is “substantially free” of these bismuth compounds if any of them are present, if at all, in an amount less than 0.01% by weight, based on the total resin solids weight of the composition, “essentially free” of these bismuth compounds if any of them are present, if at all, in trace or incidental amounts insufficient to affect any properties of the composition, such as, e.g., less than 0.001% by weight, based on the total resin solids weight of the composition, and “completely free” of these bismuth compounds if they are not present in the composition, i.e., 0.000% by weight, based on the total resin solids weight of the composition.

[0047] The electrodepositable coating composition further comprises an acid scavenger, a metal oxide, and / or a metal acetate.

[0048] As used herein, “acid scavenger” refers to pigments capable of absorbing acidity from a composition. The acid scavenger may comprise a hydrotalcite. As used herein, “hydrotalcite” refers to a magnesium-based, double layered hydroxide pigment that is capable ofabsorbing acidity in a composition. Hydrotalcite may have the general formula Mg6AhCO3(OH)i6-4H2O. Various treated and synthetic analogues of hydrotalcite are also with the scope of the present disclosure. A suitable commercially available hydrotalcite is HYCITE 713, commercially available from BASF. The hydrotalcite may be substantially free of divalent metals other than magnesium, such as zinc, calcium, and strontium. “Substantially free” in the context of these metals means that any presence of such metal is due to an impurity. The hydrotalcite may have more than one magnesium atom per molecule of hydrotalcite, such as two to six magnesium atoms.

[0049] The acid scavenger, such as hydrotalcite, may be present in an amount of at least 0.05% by weight, such as at least 0.1% by weight, such as at least 0.3% by weight, such as at least 0.5% by weight, such as at least 0.7% by weight, such as at least 0.9% by weight, based on the total resin solids weight. The acid scavenger may be present in an amount of no more than 2.0% by weight, such as no more than 1.5% by weight, such as no more than 1.0% by weight, such as no more than 0.7% by weight, such as no more than 0.5% by weight, based on the total resin solids weight. The acid scavenger may be present in an amount of 0.05% to 2.0% by weight, such as 0.05% to 1.5% by weight, such as 0.05% to 1.0% by weight, such as 0.05% to 0.7% by weight, such as 0.05% to 0.5% by weight, such as 0.1% to 2.0% by weight, such as 0.1% to 1.5% by weight, such as 0.1% to 1.0% by weight, such as 0.1% to 0.7% by weight, such as 0.1% to 0.5% by weight, such as 0.3% to 2% by weight, such as 0.3% to 1.5% by weight, such as 0.3% to 1.0% by weight, such as 0.3% to 0.7% by weight, such as 0.3% to 0.5% by weight, such as 0.5% to 2.0% by weight, such as 0.5% to 1.5% by weight, such as 0.5% to 1.0% by weight, such as 0.5% to 0.7% by weight, such as 0.7% to 2.0% by weight, such as 0.7% to 1.5% by weight, such as 0.7% to 1.0% by weight, such as 0.9% to 2.0% by weight, such as 0.9% to 1.5% by weight, such as 0.9% to 1.0% by weight, based on the total resin solids weight.

[0050] In addition to, or instead of, an acid scavenger, the present compositions may comprise a metal oxide and / or a metal acetate. As used herein, “metal acetate” or any species thereof, includes any hydrate form of the acetate. Suitable metal oxides include magnesium oxide, zinc oxide, lanthanum oxide, and / or yttrium oxide. Suitable metal acetates include magnesium acetate, zinc acetate, calcium acetate, and / or lanthanum acetate. Magnesium acetate, such as magnesium acetate tetrahydrate, is particularly suitable.

[0051] The magnesium oxide may be present in an amount of at least 0.01% by weight, such as at least 0.05% by weight, such as at least 0.1% by weight, based on resin solids weight. The magnesium oxide may be present in an amount of no more than 0.5% by weight, such as no more than 0.3% by weight, such as no more than 0.1% by weight, based on resin solids weight. The magnesium oxide may be present in an amount of 0.01% to 0.5% by weight, such as 0.01% to 0.3% by weight, such as 0.01% to 0.1% by weight, such as 0.05% to 0.5% by weight, such as 0.05% to 0.3% by weight, such as 0.05% to 0.1% by weight, such as 0.1% to 0.5% by weight, such as 0.1% to 0.3% by weight, based on resin solids weight.

[0052] The zinc oxide may be present in an amount of at least 0.15% by weight, such as at least 0.5% by weight, such as at least 0.75% by weight, such as at least 1% by weight, based on resin solids weight. The zinc oxide may be present in an amount of no more than 1.5% by weight, such as no more than 1.2% by weight, such as no more than 1% by weight, based on resin solids weight. The zinc oxide may be present in an amount of 0.15% to 1.5% by weight, such as 0.15% to 1.2% by weight, such as 0.15% to 1% by weight, such as 0.5% to 1.5% by weight, such as 0.5% to 1.2% by weight, such as 0.5% to 1% by weight, such as 0.75% to 1.5% by weight, such as 0.75% to 1.2% by weight, such as 0.75% to 1% by weight, such as 1% to 1.5% by weight, such as 1% to 1.2% by weight, based on resin solids weight.

[0053] The lanthanum oxide may be present in an amount of at least 0.15% by weight, such as at least 0.5% by weight, such as at least 0.75% by weight, such as at least 1% by weight, based on resin solids weight. The lanthanum oxide may be present in an amount of no more than 1.5% by weight, such as no more than 1.2% by weight, such as no more than 1% by weight, based on resin solids weight. The lanthanum oxide may be present in an amount of 0.15% to 1.5% by weight, such as 0.15% to 1.2% by weight, such as 0.15% to 1% by weight, such as 0.5% to 1.5% by weight, such as 0.5% to 1.2% by weight, such as 0.5% to 1% by weight, such as 0.75% to 1.5% by weight, such as 0.75% to 1.2% by weight, such as 0.75% to 1% by weight, such as 1% to 1.5% by weight, such as 1% to 1.2% by weight, based on resin solids weight.

[0054] The yttrium oxide may be present in an amount of at least 0.15% by weight, such as at least 0.5% by weight, such as at least 0.75% by weight, such as at least 1% by weight, based on resin solids weight. The yttrium oxide may be present in an amount of no more than 1.5% by weight, such as no more than 1.2% by weight, such as no more than 1% by weight, based on resin solids weight. The yttrium oxide may be present in an amount of 0.15% to 1.5%by weight, such as 0.15% to 1.2% by weight, such as 0.15% to 1% by weight, such as 0.5% to 1.5% by weight, such as 0.5% to 1.2% by weight, such as 0.5% to 1% by weight, such as 0.75% to 1.5% by weight, such as 0.75% to 1.2% by weight, such as 0.75% to 1% by weight, such as 1% to 1.5% by weight, such as 1% to 1.2% by weight, based on resin solids weight.

[0055] The magnesium acetate may be present in an amount of at least 0.1% by weight, such as at least 0.5% by weight, such as at least 1.0% by weight, such as at least 1.5% by weight, such as at least 2.0% by weight, such as at least 2.5% by weight, based on resin solids weight. The magnesium acetate may be present in an amount of no more than 3.0% by weight, such as no more than 2.0% by weight, such as no more than 1.5% by weight, such as no more than 1.0% by weight, based on resin solids weight. The magnesium acetate may be present in an amount of 0.1% to 3.0% by weight, such as 0.1% to 2.0% by weight, such as 0.1% to 1.5% by weight, such as 0.1% to 1.0% by weight, such as 0.5% to 3.0% by weight, such as 0.5% to 2.0% by weight, such as 0.5% to 1.5% by weight, such as 0.5% to 1.0% by weight, such as 1.0% to 3.0% by weight, such as 1.0% to 2.0% by weight, such as 1.0% to 1.5% by weight, such as 1.5% to 3.0% by weight, such as 1.5% to 2.0% by weight, such as 2.0% to 3.0% by weight, such as 2.5% to 3.0% by weight, based on resin solids weight.

[0056] The zinc acetate may be present in an amount of at least 0.1% by weight, such as at least 0.5% by weight, such as at least 1% by weight, such as at least 1.5% by weight, such as at least 2% by weight, such as at least 2.5% by weight, based on resin solids weight. The zinc acetate may be present in an amount of no more than 3% by weight, such as no more than 2% by weight, such as no more than 1.5% by weight, such as no more than 1% by weight, based on resin solids weight. The zinc acetate may be present in an amount of 0.1% to 3% by weight, such as 0.1% to 2% by weight, such as 0.1% to 1.5% by weight, such as 0.1% to 1% by weight, such as 0.5% to 3% by weight, such as 0.5% to 2% by weight, such as 0.5% to 1.5% by weight, such as 0.5% to 1% by weight, such as 1% to 3% by weight, such as 1% to 2% by weight, such as 1% to 1.5% by weight, such as 1.5% to 3% by weight, such as 1.5% to 2% by weight, such as 2% to 3% by weight, such as 2.5% to 3% by weight, based on resin solids weight.

[0057] The calcium acetate may be present in an amount of at least 0.1% by weight, such as at least 0.5% by weight, such as at least 1% by weight, such as at least 1.5% by weight, such as at least 2% by weight, such as at least 2.5% by weight, based on resin solids weight. The calcium acetate may be present in an amount of no more than 3% by weight, such as no morethan 2% by weight, such as no more than 1.5% by weight, such as no more than 1% by weight, based on resin solids weight. The calcium acetate may be present in an amount of 0.1% to 3% by weight, such as 0.1% to 2% by weight, such as 0.1% to 1.5% by weight, such as 0.1% to 1% by weight, such as 0.5% to 3% by weight, such as 0.5% to 2% by weight, such as 0.5% to 1.5% by weight, such as 0.5% to 1% by weight, such as 1% to 3% by weight, such as 1% to 2% by weight, such as 1% to 1.5% by weight, such as 1.5% to 3% by weight, such as 1.5% to 2% by weight, such as 2% to 3% by weight, such as 2.5% to 3% by weight, based on resin solids weight.

[0058] The lanthanum acetate may be present in an amount of at least 0.1% by weight, such as at least 0.5% by weight, such as at least 1% by weight, such as at least 1.5% by weight, such as at least 2% by weight, such as at least 2.5% by weight, based on resin solids weight. The lanthanum acetate may be present in an amount of no more than 3% by weight, such as no more than 2% by weight, such as no more than 1.5% by weight, such as no more than 1% by weight, based on resin solids weight. The lanthanum acetate may be present in an amount of 0.1% to 3% by weight, such as 0.1% to 2% by weight, such as 0.1% to 1.5% by weight, such as 0.1% to 1% by weight, such as 0.5% to 3% by weight, such as 0.5% to 2% by weight, such as 0.5% to 1.5% by weight, such as 0.5% to 1% by weight, such as 1% to 3% by weight, such as 1% to 2% by weight, such as 1% to 1.5% by weight, such as 1.5% to 3% by weight, such as 1.5% to 2% by weight, such as 2% to 3% by weight, such as 2.5% to 3% by weight, based on resin solids weight.

[0059] The electrodepo sitable coating composition may further comprise a pigment. The pigment may comprise iron oxides, lead oxides, strontium chromate, carbon black, coal dust, titanium dioxide, talc, barium sulfate, thermally conductive, electrically insulative filler materials, thermally conductive, electrically conductive filler materials, non-thermally conductive, electrically insulative filler materials, fire-retardant pigments, as well as color pigments such as cadmium yellow, cadmium red, chromium yellow and the like. As used herein, a “fire-retardant pigment” refers to a pigment that slows down or stops the spread of fire or reduces its intensity. Examples include inorganic pigments and minerals, such as those described in WO 2024 / 020483 at

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

[0060] The pigment may comprise a plate-like pigment, such as an inorganic plate-like pigment. As used herein, the term “plate-like pigment” refers to pigments having a generally platy shape.

[0061] The plate-like pigment may be a phyllosilicate pigment. As used herein, the term “phyllosilicate” refers to a group of minerals having sheets of silicates having a basic structure based on interconnected six membered rings of SiOT4tetrahedra that extend outward in infinite sheets where 3 out of the 4 oxygens from each tetrahedra are shared with other tetrahedra resulting in phyllosilicates having the basic structural unit of SiiOs'2. Phyllosilicates may comprise hydroxide ions located at the center of the tetrahedra and / or cations such as, for example, Fe+2, Mg+2, or Al+3, that form cation layers between the silicate sheets where the cations may coordinate with the oxygen of the silicate layer and / or the hydroxide ions. The phyllosilicate may have a 1:1 layer structure having one tetrahedral and one octahedral sheet per clay layer. The term “phyllosilicate pigment” refers to pigment materials comprising phyllosilicates. Phyllosilicate pigments include the micas, chlorites, serpentine, talc, and clay minerals. The clay minerals include, for example, kaolin clay. The sheet-like structure of the phyllosilicate pigment tends to result in pigment having a plate-like structure, although the pigment can be manipulated (such as through mechanical means) to have other particle structures. These pigments, when exposed to liquid media, may or may not swell and may or may not have leachable components (e.g.: ions that may be drawn towards the liquid media).

[0062] The plate-like pigment may comprise a plate-like mica pigment, a plate-like chlorite pigment, a plate-like serpentine pigment, a plate-like talc pigment, and / or a plate-like clay pigment. The plate-like clay pigment may comprise kaolin clay.

[0063] The pigment component comprising a plate-like pigment may have an average equivalent spherical diameter of at least 50 nm and up to 25 microns or higher. The averageequivalent spherical diameter as reported herein is determined using dynamic light scattering, such as with a SEDIGRAPH III PLUS particle size analyzer, available from Micromeritics Instrument Corp. As plate-like particles the pigment often has substantially opposing surfaces and particles typically exhibit an aspect ratio of the longest axis to the shortest axis of, for example, at least 2:1, such as at least 4:1, such as at least 6:1, such as at least 8:1, such as at least 10:1 or higher. For example, the plate-like pigment may have an average equivalent spherical diameter of at least 50 nm, such as at least 0.2 microns, such as at least 0.4 microns, such as at least 0.6 microns, such as at least 1 micron, such as at least 2 microns, such as at least 3 microns, such as at least 4 microns, such as at least 5 microns. The plate-like pigment may have an average equivalent spherical diameter of no more than 25 microns, such as no more than 15 microns, such as no more than 10 microns, such as no more than 5 microns, such as no more than 3.5 microns, such as no more than 2.5 microns, such as no more than 1.9 microns, such as no more than 1.5 microns, such as no more than 1 microns.

[0064] The pigment-to-binder (P:B) ratio as set forth in this disclosure refers to the weight ratio of the pigment-to-binder in the electrodepo sitable coating composition. The pigment-to-binder (P:B) ratio of the pigment to the electrodepositable binder may be at least 0.05:1, such as at least 0.1:1, such as at least 0.2:1, such as at least 0.3:1, such as at least 0.35:1, such as at least 0.4:1, such as at least 0.5:1, such as at least 0.6:1, such as at least 0.67, such as at least 0.7:1, such as at least 0.75:1, such as at least 1:1, such as at least 1.25:1, such as at least 1.5:1. The pigment-to-binder (P:B) ratio of the pigment to the electrodepositable binder may be no more than 2:1, such as no more than 1.75:1, such no more than 1.5:1, such as no more than 1.25:1, such as no more than 1:1, such as no more than 0.75:1, such as no more than 0.7:1, such as no more than 0.6:1, such as no more than 0.55: 1, such as no more than 0.5:1, such as no more than 0.25:1. The pigment-to-binder (P:B) ratio of the pigment to the electrodepositable binder may be 0.05:1 to 2:1, such as 0.05:1 to 1:1, such as 0.05:1 to 0.75:1, such as 0.05:1 to 0.7:1, such as 0.05:1 to 0.6:1, such as 0.05:1 to 0.55:1, such as 0.05:1 to 0.5:1, such as 0.05 to 0.25:1, such as 0.1:1 to 2:1, such as 0.1:1 to 1:1, such as 0.1:1 to 0.75:1, such as 0.1:1 to 0.7:1, such as 0.1:1 to 0.6:1, such as 0.1:1 to 0.55:1, such as 0.1:1 to 0.5:1, such as 0.1:1 to 0.25:1, such as 0.2:1 to 2:1, such as 0.2:1 to 1:1, such as 0.2:1 to 0.75:1, such as 0.2:1 to 0.7:1, such as 0.2:1 to 0.6:1, such as 0.2:1 to 0.55:1, such as 0.2:1 to 0.5:1, such as 0.2:1 to 0.25:1, such as 0.3:1 to 2:1, 0.3:1 to 1:1, such as 0.3:1 to 0.75:1, such as 0.3:1 to 0.7:1, such as 0.3:1 to 0.6:1, such as 0.3:1 to0.55:1, such as 0.3:1 to 0.5:1, such as 0.4:1 to 2:1, such as 0.4:1 to 1.75:1, such as 0.4:1 to 1.5:1, such as 0.4:1 to 1.25:1, such as 0.4:1 to 1:1, such as 0.4:1 to 0.75:1, such as 0.4:1 to 0.7:1, such as 0.4:1 to 0.6:1, such as 0.4:1 to 0.55:1, such as 0.4:1 to 0.5:1, such as 0.5:1 to 2:1, such as 0.5:1 to 1.75:1, such as 0.5:1 to 1.50:1, such as 0.5:1 to 1.25:1, such as 0.5:1 to 1:1, such as 0.5:1 to 0.75:1, such as 0.5:1 to 0.7:1, such as 0.5:1 to 0.6:1, such as 0.5:1 to 0.55:1, such as 0.6:1 to 2:1, such as 0.6:1 to 1.75:1, such as 0.6:1 to 1.5:1, such as 0.6:1 to 1.25:1, such as 0.6:1 to 1:1, such as 0.6:1 to 0.75:1, such as 0.6:1 to 0.7:1, such as 0.67:1 to 2:1, such as 0.67:1 to 1.75:1, such as 0.67:1 to 1.5:1, such as 0.67:1 to 1.25:1, such as 0.67:1 to 1:1, such as 0.67:1 to 0.75:1, such as 0.67:1 to 0.7:1, such as 0.7:1 to 2:1, such as 0.7:1 to 1.75:1, such as 0.7:1 to 1.5:1, such as 0.7:1 to 1.25:1, such as 0.7:1 to 1:1, such as 0.7:1 to 0.75:1, such as 0.75:1 to 2:1, such as 0.75:1 to 1.75:1, such as 0.75:1 to 1.5:1, such as 0.75:1 to 1.25:1, such as 0.75:1 to 1:1, such as 1:1 to 2:1, such as 1:1 to 1.75:1, such as 1:1 to 1.5:1, such as 1:1 to 1.25:1, such as 1.25:1 to 2:1, such as 1.25:1 to 1.75:1, such as 1.25:1 to 1.5:1, such as 1.5:1 to 2:1, such as 1.5:1 to 1.75:1.

[0065] The pigment-to-binder (P:B) ratio of the inorganic plate-like pigment to the electrodepositable binder may be at least 0.4:1, such as at least 0.5:1, such as at least 0.6:1, such as at least 0.75:1, such as at least 1:1, such as at least 1.25:1, such as at least 1.5:1. The pigment- to-binder (P:B) ratio of the inorganic plate-like pigment to the electrodepositable binder may be no more than 2:1, such as no more than 1.75:1, such no more than 1.5:1, such as no more than 1.25:1, such as no more than 1:1, such as no more than 0.75:1, such as no more than 0.7:1, such as no more than 0.6:1, such as no more than 0.55: 1, such as no more than 0.5:1. The pigment-to- binder (P:B) ratio of the inorganic plate-like pigment to the electrodepositable binder may be 0.4:1 to 2:1, such as 0.4:1 to 1.75:1, such as 0.4:1 to 1.5:1, such as 0.4:1 to 1.25:1, such as 0.4:1 to 1:1, such as 0.4:1 to 0.75:1, such as 0.4:1 to 0.7:1, such as 0.4:1 to 0.6:1, such as 0.4:1 to 0.55:1, such as 0.4:1 to 0.5:1, such as 0.5:1 to 2:1, such as 0.5:1 to 1.75:1, such as 0.5:1 to 1.50:1, such as 0.5:1 to 1.25:1, such as 0.5:1 to 1:1, such as 0.5:1 to 0.75:1, such as 0.5:1 to 0.7:1, such as 0.5:1 to 0.6:1, such as 0.5:1 to 0.55:1, such as 0.6:1 to 2:1, such as 0.6:1 to 1.75:1, such as 0.6:1 to 1.5:1, such as 0.6:1 to 1.25:1, such as 0.6:1 to 1:1, such as 0.6:1 to 0.75:1, such as 0.6:1 to 0.7:1, such as 0.75:1 to 2:1, such as 0.75:1 to 1.75:1, such as 0.75:1 to 1.5:1, such as 0.75:1 to 1.25:1, such as 0.75:1 to 1:1, such as 1:1 to 2:1, such as 1:1 to 1.75:1, such as 1:1 to 1.5:1, such as 1:1 to 1.25:1, such as 1.25:1 to 2:1, such as 1.25:1 to 1.75:1, such as 1.25:1 to 1.5:1, such as 1.5:1 to 2:1, such as 1.5:1 to 1.75:1.

[0066] The pigment may be added without using a separately made pigment paste. For example, the pigment may be dispersed directly into the cationic salt group-containing filmforming polymer comprising active hydrogen functional groups and / or the blocked polyisocyanate curing agent using conventional grinding techniques.

[0067] The pigmented electrodepo sitable coating composition may be formed without using a pigment paste by the steps of (1) heating an unneutralized cationic salt forming group- containing, film-forming polymer to an elevated temperature; (2) optionally adding a dispersing agent to the unneutralized cationic salt forming group-containing, film-forming polymer with agitation to form a mixture; (3) adding the pigment to the mixture at elevated temperature with agitation; and (4) dispersing the mixture of the cationic salt forming group-containing, filmforming polymer, the pigment, and dispersing agent (if present) into an aqueous medium comprising water and a neutralizing acid with agitation, wherein cationic salt forming groups in the cationic salt forming group-containing, film-forming polymer are neutralized by the neutralizing acid to form a cationic salt group-containing film forming polymer. As used herein, the term “dispersing agent” refers to a material capable of promoting dispersion of the pigment into the resinous phase of the electrodepositable coating composition, including, but not limited to, an acid.

[0068] When pigment is incorporated into the electrodepositable coating composition without using a pigment paste, the electrodepositable coating composition may be substantially free, essentially free, or completely free of a grind resin. As used herein, an electrodepositable coating composition is “substantially free”, “essentially free”, or “completely free” of grind resin if grind resin is present, if at all, in an amount of no more than 5% by weight, or no more than 3% by weight, or 0.0 wt%, respectively, based on the total resin solids weight of the composition. As used herein, the term “grind resin” refers to a cationic salt group-containing resin that is used during milling of the pigment to wet and charge the pigment surface. Although the grind resin may be the same as the film- forming polymer described above, and / or may react into the film, it is not considered pail of the electrodepositable binder. Suitable grind resins include resins comprising sulfonium, quaternary ammonium, or amine-salt groups.

[0069] Alternatively, the pigment may be added via a pigment paste. As used herein, the term “pigment paste” refers to a combination of one or more pigment(s) with a grind resindistinct from the main film-forming polymer and, optionally, additives such as wetting or dispersing aids to assist in dispersing the pigment and other optional filler materials if present.

[0070] Suitable dispersing aids include dispersing acids, such as those that may comprise a first acidic proton having a pKa of at least 1.1, such as at least 1.5 or 1.8, but no more than 4.6, such as 4.0 or less or 3.5 or less. Suitable ranges include 1.1 to 4.6, 1.5 to 4.9 and 1.8 to 3.5. A dispersing acid may comprise an oxyacid of phosphorous, such as phosphoric acid and / or phosphonic acid; “dispersing acid” as used herein includes the salts thereof.

[0071] Alternatively, the electrodepositable coating compositions may be substantially free, essentially free, or completely free of a dispersing acid, such as an oxyacid of phosphorus. As used herein, an electrodepositable coating composition is “substantially free” or “essentially free” of dispersing acid if the dispersing acid is present, if at all, in an amount of less than 0.10% by weight or less than 0.05% by weight, respectively, based on the total solids weight of the composition. As used herein, an electrodepositable coating composition is “completely free” of dispersing acid, such as a phosphorus acid, if the dispersing acid is not present, i.e., less than 0.001% by weight, based on the total solids weight of the composition.

[0072] The present disclosure is further directed to pigment pastes, particularly those that may be used electrodepositable coating compositions.

[0073] Accordingly, the present disclosure is further directed to a pigment paste comprising a grind resin; and a pigment component comprising a plate-like pigment and an acid scavenger, metal oxide, and / or a metal acetate, wherein the plate-like pigment is present in an amount of at least 50% by weight, based on the total weight of pigment in the pigment component, such as at least 60% by weight, such as at least 80% by weight, or such as at least 90% by weight. The pigment may comprise a plate-like pigment in an amount of 50% to 90% by weight, such as 50% to 80% by weight, such as 50% to 60% by weight, such as 60% to 90% by weight, such as 60% to 80% by weight, such as 80% to 90% by weight, based on the total weight of the pigment in the pigment component. Any of the plate-like pigments and acid scavengers, metal oxides and metal acetates described above may be used.

[0074] The pigment paste may further comprise a bismuth catalyst comprising solubilized bismuth, such as, for example, bismuth methane sulphonate, bismuth ethane sulphonate, or a combination thereof.

[0075] The present disclosure is also directed to a pigment paste for an electrodepo sitable coating composition comprising a cationic salt group-containing resin; a bismuth catalyst; and a pigment comprising an acid scavenger, metal oxide, and / or metal acetate, and when the acid scavenger comprises hydrotalcite, the hydrotalcite is substantially free of divalent metals other than magnesium, and / or the hydrotalcite has more than one magnesium atom per molecule of hydrotalcite.

[0076] The paste may further comprise a plate-like pigment, which may be present in any amount, such as at least 50% by weight, based on the total weight of pigment in the paste, such as at least 60% by weight, such as at least 80% by weight, such as at least 90% by weight. The paste may comprise a plate-like pigment in an amount of 50% to 90% by weight, such as 50% to 80% by weight, such as 50% to 60% by weight, such as 60% to 90% by weight, such as 60% to 80% by weight, such as 80% to 90% by weight, based on the total weight of the pigment.

[0077] When the pigment pastes of the present disclosure comprise a bismuth catalyst, bismuth metal from the curing catalyst may be present in an amount of greater than 3% by weight, based on resin solids weight, such as at least 5% by weight, such as at least 7% by weight, such as at least 9% by weight. The bismuth metal from the curing catalyst may be present in an amount of greater than 3% to 20% by weight, such as greater than 3% to 15% by weight, such as greater than 3% to 10% by weight, such as 5% to 20% by weight, such as 5% to 15% by weight, such as 5% to 10% by weight, such as 7% to 20% by weight, such as 7% to 15% by weight, such as 7% to 10% by weight, such as 9% to 20% by weight, such as 9% to 15% by weight, such as 9% to 10% by weight, based on resin solids weight.

[0078] The grind resin may comprise a cationic salt group-containing resin, such as one comprising sulfonium, quaternary ammonium, or amine-salt groups. The grind resin may be present in the pigment pastes described herein in an amount suitable for forming a pigment paste. The grind resin may be present in an amount of such that the weight ratio of pigment to grind resin is at least 0.5:1, such as at least 1:1, such as at least 1.5:1, such as at least 2.5:1, such as at least 4:1, such as at least 5:1. The grind resin may be present in an amount of such that the weight ratio of pigment to grind resin is no more than 20: 1, such as no more than 10: 1, such as no more than 6:1, such as no more than 3:1, such as no more than 2.5:1, such as no more than 2:1. The grind resin may be present in an amount of such that the weight ratio of pigment to grind resin is 0.5:1 to 20:1, such as 0.5:1 to 10:1, such as 0.5:1 to 6:1, such as 0.5:1 to 3:1, suchas 0.5:1 to 2.5:1, such as 0.5:1 to 2:1, such as 1: 1 to 20:1, such as 1:1 to 10:1, such as 1:1 to 6:1, such as 1:1 to 3:1, such as 1:1 to 2.5:1, such as 1:1 to 2:1, such as 1.5:1 to 20:1, such as 1.5:1 to 10:1, such as 1.5:1 to 6:1, such as 1.5:1 to 3:1, such as 1.5:1 to 2.5:1, such as 1.5:1 to 2:1, such as 2.5:1 to 20:1, such as 2.5:1 to 10:1, such as 2.5:1 to 6:1, such as 2.5:1 to 3:1, such as 4:1 to 20:1, such as 4:1 to 10:1, such as 4:1 to 6:1, such as 5:1 to 20:1, such as 5:1 to 10:1, such as 5:1 to 6:1.

[0079] The grind resin may be present in the pigment pastes of the present disclosure in an amount of at least 4.8% by weight, such as at least 9% by weight, such as at least 14.3% by weight, such as at least 25% by weight, such as at least 28.6% by weight, such as at least 33.3% by weight, based on the total weight of the grind resin and pigment. The grind resin may be present in the pigment paste in an amount of no more than 66.7% by weight, such as no more than 50% by weight, such as no more than 40% by weight, such as no more than 28.6% by weight, such as no more than 20% by weight, such as no more than 16.7% by weight, such as no more than 9% by weight, such as no more than 4.8% by weight, based on the total weight of the grind resin and pigment. The grind resin may be present in the pigment paste in an amount of 4.8% to 66.7% by weight, such as 4.8% to 50% by weight, such as 4.8% to 40% by weight, such as 4.8% to 28.6% by weight, such as 4.8% to 20% by weight, such as 4.8% to 16.7% by weight, such as 4.8% to 9% by weight, such as 9% to 66.7% by weight, such as 9% to 50% by weight, such as 9% to 40% by weight, such as 9% to 28.6% by weight, such as 9% to 20% by weight, such as 9% to 16.7% by weight, such as 14.3% to 66.7% by weight, such as 14.3% to 50% by weight, such as 14.3% to 40% by weight, such as 14.3% to 28.6% by weight, such as 14.3% to 20% by weight, such as 14.3% to 16.7% by weight, such as 25% to 66.7% by weight, such as 25% to 50% by weight, such as 25% to 40% by weight, such as 25% to 28.6% by weight, such as 28.6% to 66.7% by weight, such as 28.6% to 50% by weight, such as 28.6% to 40% by weight, such as 33.3% to 66.7% by weight, such as 33.3% to 50% by weight, such as 33.3% to 40% by weight, based on the total weight of the grind resin and pigment.

[0080] The acid scavenger, metal oxide and metal acetate used in the pigment pastes of the present disclosure may comprise any of those described above, such as a hydrotalcite and magnesium acetate.

[0081] The pigment pastes of the present disclosure may comprise other additive resinous materials, such as wetting or dispersing aids, plasticizers, and the like. These additiveresinous materials are distinct from the grind resin in that they do not include a cationic salt group.

[0082] The pigment pastes may be substantially free, essentially free, or completely free of a curing agent, including a blocked polyisocyanate curing agent. As used herein, a pigment paste is “substantially free” or “essentially free” of curing agent if curing agent is present, if at all, in an amount of less than 10% by weight or less than 5% by weight, respectively, based on resin solids weight. As used herein, a pigment paste is “completely free” of curing agent if curing agent is not present in the pigment paste, i.e., 0% by weight, based on resin solids weight. Although the grind resin may be the same as the film-forming polymer described above, and / or may react into the film, it is not considered part of the electrodepositable binder.

[0083] The present disclosure is also directed to electrodepositable coating compositions comprising an electrodepositable binder, and any of the pigment pastes described herein. The electrodepositable binder may be any of those described herein or otherwise known in the art. For example, the electrodepositable binder may comprise a cationic salt group-containing filmforming polymer comprising active hydrogen functional groups, and a blocked polyisocyanate curing agent comprising blocking groups. The blocking groups of the blocked polyisocyanate may comprise any suitable blocking group, such as blocking groups comprising a 1,2-polyol as a blocking agent.

[0084] According to the present disclosure, any of the electrodepositable coating compositions described herein may comprise other ingredients, such as fillers, plasticizers, corrosion inhibitors, antioxidants, biocides, UV light absorbers and stabilizers, hindered amine light stabilizers, defoamers, fungicides, dispersing aids, flow control agents, surfactants, wetting agents, or combinations thereof. Alternatively, the electrodepositable coating composition may be completely free of any of these other ingredients, i.e., the optional ingredient is not present in the electrodepositable coating composition. When used, these other ingredients may be present in the electrodepositable coating compositions in amounts of 0.01% to 3% by weight, based on total weight of the resin solids of the electrodepositable coating composition, either cumulatively or respectively.

[0085] Any of the electrodepositable coating compositions of the present disclosure may have a concentration of phosphate ions of less than 5 ppm, such as less than 3 ppm or less than 1 ppm. As used herein, “phosphate ions” refers to anions having the general chemical formula[PO4]3', [HPO4]2', [H2PO4]', [RPCh]2' and / or [ RH PO31|_. Phosphate ions may be introduced into the coating compositions through numerous sources, such as dispersing acids, or through carryover from phosphate containing pretreatment. Phosphate ions can also come in through certain pigments, such as clays.

[0086] According to the present disclosure, the electrodepositable coating composition may comprise water and / or one or more organic solvent(s). Water can, for example, be present in amounts of 40% to 90% by weight, such as 50% to 75% by weight, based on total weight of the electrodepositable coating composition. Examples of suitable organic solvents include oxygenated organic solvents, such as monoalkyl ethers of ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol which contain from 1 to 10 carbon atoms in the alkyl group, such as the monoethyl and monobutyl ethers of these glycols. Examples of other at least partially water-miscible solvents include alcohols such as ethanol, isopropanol, butanol and diacetone alcohol. If used, the organic solvents may typically be present in an amount of less than 10% by weight, such as less than 5% by weight, based on total weight of the electrodepositable coating composition. The electrodepositable coating composition may, in particular, be provided in the form of a dispersion, such as an aqueous dispersion.

[0087] According to the present disclosure, the total solids content of the electrodepositable coating composition may be at least 1% by weight, such as at least 5% by weight, and may be no more than 50% by weight, such as no more than 40% by weight, such as no more than 25% by weight, based on the total weight of the electrodepositable coating composition. The total solids content of the electrodepositable coating composition may be 1% to 50% by weight, such as 5% to 40% by weight, such as 5% to 25% by weight, based on the total weight of the electrodepositable coating composition. As used herein, “total solids” refers to the non-volatile content of the electrodepositable coating composition, i.e., materials which will not volatilize when heated to 110°C for 15 minutes.

[0088] Any of the electrodepositable coating compositions and pigment pastes of the present invention may be substantially free, essentially free, or completely free of metal oxides comprising zinc oxide, lanthanum oxide, yttrium oxide, and / or magnesium oxide. As used in conjunction with these specific oxide compounds, substantially free means less than 0.5 wt% and essentially free means less than 0.3 wt%, with wt% based on total resin solids, and completely free means that any of these oxides are present only through an impurity in trace amounts.

[0089] The present disclosure is further directed to a method for using any of the electrodepositable coating compositions described herein to coat a substrate by electrodeposition of the coating composition onto at least a portion of the substrate. The electrodepositable coating composition may be electrocoated onto an electroconductive substrate and at least partially cured using application conditions, times, and temperatures, known to those skilled in the art.

[0090] The substrate optionally may be pretreated with a pretreatment composition prior to applying the electrodeposited coating. Any suitable pretreatment can be used. The pretreatment solution may be a non-metal phosphate pretreatment composition, such as a zirconium-containing pretreatment composition. Suitable zirconium-containing pretreatment compositions include those described in U.S. Pat. No. 7,749,368, at col. 3, line 24 through col. 6, line 48, and U.S. Pat. No. 8,673,091, at col. 3, line 18 through col. 8, line 55, the cited portion of which from each are incorporated herein by reference.

[0091] A “pretreatment composition” refers to a composition that can react with and chemically altering the substrate surface and binding to it to form a layer that affords corrosion protection. A “non-metal phosphate pretreatment composition” refers to pretreatment compositions wherein a metal phosphate compound, such as zinc phosphate or iron phosphate, is not the primary active compound in the pretreatment composition. Alternatively, zinc phosphate pretreatment compositions, such as, for example, those described in U.S. Pat. No. 4,793,867, at col. 3, line 5 through col. 5, line 8 and col. 5, line 64 through col. 11, line 50, and U.S. Pat. No. 5,588,989, at col. 2, line 20 through col. 4, line 47, the cited portion of which for each is incorporated herein by reference, can be used.

[0092] The non-metal phosphate pretreatment composition, such as the zirconium- containing pretreatment composition, may be substantially free, essentially free, or completely free of phosphate. As used herein, a non-metal phosphate pretreatment composition is “substantially free” or “essentially free” of phosphate if it comprises less than 1% by weight or less than 0.5% by weight of phosphate, respectively, based on the total weight of the non-metal phosphate pretreatment composition. As used herein, a non-metal phosphate pretreatment composition is “completely free” of phosphate if phosphate is not present, 0% by weight phosphate, based on the total weight of the non-metal phosphate pretreatment composition.

[0093] The cationic electrodepositable coating composition of the present disclosure may be deposited upon an electrically conductive substrate by placing the composition in contact withan electrically conductive cathode and an electrically conductive anode, with the surface to be coated being the cathode. Following contact with the composition, an adherent coating of the coating composition may be deposited on the cathode when a sufficient voltage is impressed between the electrodes.

[0094] The applied voltage in the electrophoretic application of the electrodepositable coating compositions of the present disclosure may be varied and may be, for example, as low as one volt to as high as several thousand volts, such as between 50 and 500 volts. The current density may, for example, be between 0.5 ampere and 15 amperes per square foot, and tends to decrease during electrodeposition indicating the formation of an insulating coating.

[0095] Following application of the electrodepositable coating composition, the substrate may be heated to a temperature and for a time sufficient to at least partially cure the electrodeposited coating on the substrate. As used herein, the term “at least partially cure” refers to subjecting the coating composition to curing conditions such that at least a portion of the reactive groups of the components of the coating composition cure or crosslink to form a coating. In general, the substrate may be heated to a temperature ranging from 250°F to 450°F (121.1°C to 232.2°C), such as from 275°F to 400°F (135°C to 204.4°C), such as from 300°F to 360°F (149°C to 180°C). For purposes of the present disclosure, all that is necessary is that the time be sufficient to effect cure of the coating on the substrate. The curing time may, for example, range from 10 minutes to 60 minutes, such as 20 to 40 minutes. The thickness of the resultant cured electrodeposited coating is not limited and may range from 15 to 50 microns.

[0096] The present disclosure is also directed to substrates coated by the methods of coating a substrate disclosed herein. Suitable substrates include electroconductive substrates, such as metal substrates, metal alloy substrates, and / or substrates that have been metallized, such as nickel-plated plastic. The metal or metal alloy can comprise or be steel, aluminum, zinc, nickel, and / or magnesium. For example, the steel substrate could be cold rolled steel, hot rolled steel, electrogalvanized steel, and / or hot dipped galvanized steel. Aluminum alloys of the 1XXX, 2XXX, 3XXX, 4XXX, 5XXX, 6XXX, or 7XXX series as well as clad aluminum alloys also may be used as the substrate. Aluminum alloys may comprise, for example, 0.01% by weight copper to 10% by weight copper. Aluminum alloys that are treated may also include castings, such as 1XX.X, 2XX.X, 3XX.X, 4XX.X, 5XX.X, 6XX.X, 7XX.X, 8XX.X, or 9XX.X (e.g., A356.0). Magnesium alloys of the AZXX (including Eform Plus), AMXX, EVXX, ZEXX,ZCXX, HKXX, HZXX, QEXX, QHXX, WEXX, ZEK100, or Elektron 21 series also may be used as the substrate. The substrate used may also comprise titanium and / or titanium alloys, zinc and / or zinc alloys, and / or nickel and / or nickel alloys. Suitable substrates for use in the present disclosure include those that are often used in the assembly of vehicular bodies (e.g., without limitation, door, body panel, trunk deck lid, roof panel, hood, roof and / or stringers, rivets, landing gear components, and / or skins used on an aircraft), a vehicular frame, vehicular parts, motorcycles, wheels, industrial structures and components such as appliances, including washers, dryers, refrigerators, stoves, dishwashers, and the like, personal electronics, agricultural equipment, lawn and garden equipment, metal fencing, guard rails, air conditioning units, heat pump units, heat exchangers, lawn furniture, and other articles. As used herein, “vehicle” or variations thereof includes, but is not limited to, civilian, commercial and military aircraft, and / or land vehicles such as cars, motorcycles, trucks, and / or bicycles including electric bicycles. The metal substrate also may be in the form of, for example, a sheet of metal or a fabricated part.

[0097] The substrate may be a multi-metal article. As used herein, the term “multi-metal article” refers to (1) an article that has at least one surface comprised of a first metal and at least one surface comprised of a second metal that is different from the first metal, (2) a first article that has at least one surface comprised of a first metal and a second article that has at least one surface comprised of a second metal that is different from the first metal, or (3) both (1) and (2).

[0098] The substrate may comprise a battery or battery component. The battery component may comprise, but is not limited thereto, a battery cell, a battery shell, a battery module, a battery pack, a battery box, a battery cell casing, a pack shell, a battery lid and tray, a thermal management system, a battery housing, a module housing, a module racking, a battery side plate, a battery cell enclosure, a cooling module, a cooling tube, a cooling fin, a cooling plate, a bus bar, a battery frame, an electrical connection, metal wires, or copper or aluminum conductors or cables. The battery may be, for example, an electric vehicle battery, and the battery component may be, for example, an electric vehicle battery component.

[0099] The substrate may comprise a three-dimensional component formed by an additive manufacturing process such as selective laser melting, e-beam melting, directed energy deposition, binder jetting, metal extrusion, and the like. The three-dimensional component may be a metal and / or resinous component.

[0100] Additional coating layers may be added to the substrate, including any suitable additional coating layers known in the art, and each may independently be waterborne, solventborne, in solid particulate form (i.e., a powder coating composition), or in the form of a powder slurry. The additional coating layers may each be cured independently or optionally applied "wet-on- wet" and cured simultaneously. As used herein, “wet-on- wet” refers to a process, wherein a coating, for example a clear coat, is applied over a substantially uncured different coating, for example a color coat, and both coatings are then cured simultaneously. When one or more additional coating layers are used with the coating layer deposited from the electrodepositable coating compositions described herein, the coating layers may be collectively referred to as a “coating stack”.

[0101] Any numerical range recited herein is intended to include all sub-ranges subsumed therein. Singular encompasses plural and vice versa. For example, although reference is made herein to "a" film-forming polymer, “a” blocked polyisocyanate curing agent, “a” bismuth catalyst, “a” metal oxide, “a” metal acetate, “an” acid scavenger, and the like, one or more of each of these and any other components can be used. Also, as used herein, the term “polymer” refers to prepolymers, oligomers and both homopolymers and copolymers; the prefix “poly” refers to two or more. When ranges are given, any endpoints of those ranges and / or numbers within those ranges can be combined with the scope of the present disclosure. “Including”, “such as”, “for example” and like terms means “including / such as / for example but not limited to”. The terms “acrylic” and “acrylate” are used interchangeably (unless to do so would alter the intended meaning) and include acrylic acids, anhydrides, and derivatives thereof, lower alkyl-substituted acrylic acids, e.g., C1-C2 substituted acrylic acids, such as methacrylic acid, methacrylic acid, etc., and their Ci-Ce alkyl esters and hydroxyalkyl esters, unless clearly indicated otherwise.Aspects

[0102] Aspect 1. An electrodepositable coating compositions comprising a cationic salt group-containing film-forming polymer comprising active hydrogen functional groups; a blocked polyisocyanate curing agent; a bismuth catalyst; and an acid scavenger, metal oxide and / or metal acetate; with the provisos that the electrodepositable coating composition is substantially free, essentially free, or completely free of a dispersing acid comprising an oxyacid of phosphorus, the P:B of the composition is 0.2 or greater:!, and when the acid scavengercomprises hydrotalcite, the hydrotalcite is substantially free of divalent metals other than magnesium and / or the hydrotalcite has more than one magnesium atom per molecule of hydrotalcite.

[0103] Aspect 2. The electrodepo sitable coating composition of aspect 1, wherein the film-forming polymer comprises a di-epoxide.

[0104] Aspect 3. The electrodepo sitable coating composition of any preceding aspect, wherein the film-forming polymer comprises a diglycidyl ether of bisphenol A and / or a diglycidyl ether of bisphenol F.

[0105] Aspect 4. The electrodepo sitable coating composition of any preceding aspect, wherein the film-forming polymer comprises 40 to 90 wt% of the coating composition, with wt% based on total weight of the resin solids.

[0106] Aspect 5. The electrodepo sitable coating composition of any preceding aspect, wherein the blocking agent on the blocked curing agent comprises a 1,2-polyol.

[0107] Aspect 6. The electrodepo sitable coating composition of any preceding aspect, wherein the coating composition further comprises a second curing agent.

[0108] Aspect 7. The electrodepo sitable coating composition of any preceding aspect, wherein the coating composition further comprises a second curing agent comprising an aminoplast.

[0109] Aspect 8. The electrodepo sitable coating composition of any preceding aspect, wherein the curing agent comprises 10 to 60 wt% of the coating composition, with wt% based on total weight of the resin solids.

[0110] Aspect 9. The electrodepo sitable coating composition of any preceding aspect, wherein the bismuth catalyst comprises a soluble bismuth catalyst.

[0111] Aspect 10. The electrodepo sitable coating composition of any preceding aspect, wherein the coating composition comprises 10 to 20,000 ppm soluble bismuth metal introduced into the composition from the bismuth catalyst.

[0112] Aspect 11. The electrodepo sitable coating composition of any preceding aspect, wherein the bismuth catalyst comprises bismuth methane sulphonic acid.

[0113] Aspect 12. The electrodepo sitable coating composition of any preceding aspect, wherein the coating composition is substantially free, essentially free, and / or completely free of a bismuth compound having a ligand prepared from a p-diketone.

[0114] Aspect 13. The electrodepo sitable coating composition of any preceding aspect, wherein the bismuth catalyst is present in an amount of 0.01% to 3.0% by weight of bismuth metal, based on total resin solids weight of the composition.

[0115] Aspect 14. The electrodepo sitable coating composition of any preceding aspect, wherein the coating composition further comprises a co-catalyst.

[0116] Aspect 15. The electrodepo sitable coating composition of any preceding aspect, wherein the composition is substantially free, essentially free, and / or completely free of catalytic tin.

[0117] Aspect 16. The electrodepo sitable coating composition of any preceding aspect, wherein the coating composition comprises an acid scavenger comprising hydrotalcite.

[0118] Aspect 17. The electrodepo sitable coating composition of any preceding aspect, wherein the coating composition comprises an acid scavenger comprising hydrotalicte that is substantially free of zinc, calcium, strontium, lead and / or cadmium.

[0119] Aspect 18. The electrodepo sitable coating composition of any preceding aspect, wherein the coating composition comprises an acid scavenger comprising hydrotalcite having two to six magnesium atoms.

[0120] Aspect 19. The electrodepo sitable coating composition of any preceding aspect, wherein the coating composition comprises an acid scavenger comprising hydrotalcite having the formula Mg6AhCO3(OH)i6-4H2O.

[0121] Aspect 20. The electrodepo sitable coating composition of any preceding aspect, wherein the coating composition comprises an acid scavenger comprising hydrotalcite in an amount of 0.05 wt% to 2.0 wt%, based on the total resin solids weight.

[0122] Aspect 21. The electrodepo sitable coating composition of any preceding aspect, wherein the coating composition comprises a metal oxide comprising magnesium oxide.

[0123] Aspect 22. The electrodepo sitable coating composition of any preceding aspect, wherein the coating composition comprises a metal oxide comprising zinc oxide.

[0124] Aspect 23. The electrodepo sitable coating composition of any preceding aspect, wherein the coating composition comprises a metal oxide comprising lanthanum oxide.

[0125] Aspect 24. The electrodepo sitable coating composition of any preceding aspect, wherein the coating composition comprises a metal oxide comprising yttrium oxide.

[0126] Aspect 25. The electrodepo sitable coating composition of any preceding aspect, wherein the coating composition comprises a metal acetate comprising magnesium acetate.

[0127] Aspect 26. The electrodepo sitable coating composition of any preceding aspect, wherein the coating composition comprises a metal acetate comprising zinc acetate.

[0128] Aspect 27. The electrodepo sitable coating composition of any preceding aspect, wherein the coating composition comprises a metal acetate comprising calcium acetate.

[0129] Aspect 28. The electrodepo sitable coating composition of any preceding aspect, wherein the coating composition comprises a metal acetate comprising lanthanum.

[0130] Aspect 29. The electrodepo sitable coating composition of any preceding aspect, wherein the coating composition comprises a metal acetate comprising magnesium acetate tetrahydrate.

[0131] Aspect 30. The electrodepo sitable coating composition of any preceding aspect, wherein the coating composition comprises a metal acetate comprising magnesium acetate in an amount of 0.1 wt% to 3.0 wt%, based on resins solids weight.

[0132] Aspect 31. The electrodepo sitable coating composition of any preceding aspect, further comprising an electrically insulative filler.

[0133] Aspect 32. The electrodepo sitable coating composition of any of aspects 1 to30, further comprising an electrically conductive filler.

[0134] Aspect 33. The electrodepo sitable coating composition of any preceding aspect, further comprising a thermally conductive filler.

[0135] Aspect 34. The electrodepo sitable coating composition of any preceding aspect, further comprising a non-thermally conductive filler.

[0136] Aspect 35. The electrodepo sitable coating composition of any preceding aspect, further comprising a fire-retardant pigment.

[0137] Aspect 36. The electrodepo sitable coating composition of any preceding aspect, further comprising a plate-like pigment.

[0138] Aspect 37. The electrodepo sitable coating composition of any preceding aspect, further comprising a phyllosilicate pigment.

[0139] Aspect 38. The electrodepo sitable coating composition of any preceding aspect, further comprising kaolin clay.

[0140] Aspect 39. The electrodepositable coating composition of any of aspects 1 to 38, wherein the composition further comprises a plate-like pigment present in a pigment -to- binder ratio of at least 0.4: 1.

[0141] Aspect 40. The electrodepositable coating composition of any preceding aspect, further comprising a pigment, wherein the pigment is incorporated into the coating composition without the use of a pigment paste.

[0142] Aspect 41. The electrodepositable coating composition of any preceding aspect, wherein the composition is substantially free, essentially free, and / or completely free of a grind resin.

[0143] Aspect 42. A pigment paste for an electrodepositable coating composition comprising a. a grind resin comprising a cationic salt group-containing resin; and b. a pigment component comprising a plate-like pigment and an acid scavenger, a metal oxide and / or a metal acetate, wherein the plate-like pigment is present in an amount of at least 50% by weight.

[0144] Aspect 43. The pigment paste of aspect 42, wherein the metal oxide does not comprise yttrium oxide.

[0145] Aspect 44. The pigment past of aspects 42 to 43, wherein the metal oxide does not comprise zinc oxide.

[0146] Aspect 45. The pigment paste of any of aspects 42 to 44, further comprising a bismuth catalyst.

[0147] Aspect 46. A pigment paste for an electrodepositable coating composition comprising, a. a cationic salt group-containing resin; b. a bismuth catalyst; and c. a pigment component comprising an acid scavenger, metal oxide, and / or metal acetate, and when the acid scavenger comprises hydrotalcite, the hydrotalcite is substantially free of divalent metals other than magnesium, and / or the hydrotalcite has more than one magnesium atom per molecule of hydrotalcite.

[0148] Aspect 47. The pigment paste of aspect 46, further comprising a plate-like pigment.

[0149] Aspect 48. The pigment paste of any of aspects 42 to 47, wherein the paste comprises a bismuth catalyst and the bismuth metal from the catalyst is present in an amount of greater than 3% by weight, based on total solids weight.

[0150] Aspect 49. The pigment paste of any of aspects 42 to 48, wherein the paste comprises a bismuth catalyst comprising bismuth methane sulphonic acid.

[0151] Aspect 50. The pigment paste of any of aspects 42 to 49, wherein the paste is substantially free, essentially free, and / or completely free of a bismuth compound having a ligand prepared from a P-diketone.

[0152] Aspect 51. The pigment paste of any of aspects 42 to 50, wherein the paste is substantially free, essentially free, and / or completely free of catalytic tin.

[0153] Aspect 52. The pigment paste of any of aspects 42 to 51, wherein the cationic salt group- containing resin comprises sulfonium, quaternary ammonium, or amine-salt groups

[0154] Aspect 53. The pigment paste of any of aspects 42 to 52, wherein the weight ratio of pigment to grind resin is at least 0.5:1

[0155] Aspect 54. The pigment paste of any of aspects 42 to 53, wherein the weight ratio of pigment to grind resin is no more than 20: 1.

[0156] Aspect 55. The pigment paste of any of aspects 42 to 54, wherein the weight ratio of pigment to grind resin is 0.5:1 to 20: 1.

[0157] Aspect 56. The pigment paste of any of aspects 42 to 55, wherein the weight ratio of pigment to grind resin is 5: 1 to 6: 1.

[0158] Aspect 57. The pigment paste of any of aspects 42 to 56, wherein the paste is substantially free, essentially free, and / or completely free of a curing agent.

[0159] Aspect 58. The pigment paste of any of aspects 42 to 57, wherein the paste comprises an acid scavenger comprising hydrotalcite.

[0160] Aspect 59. The pigment paste of any of aspects 42 to 58, wherein the paste comprises an acid scavenger comprising hydrotalicte that is substantially free of zinc, calcium, strontium, lead and / or cadmium.

[0161] Aspect 60. The pigment paste of any of aspects 42 to 59, wherein the paste comprises an acid scavenger comprising hydrotalcite having two to six magnesium atoms.

[0162] Aspect 61. The pigment paste of any of aspects 42 to 60, wherein the pigment paste comprises an acid scavenger comprising hydrotalcite having the formula Mg6A12CO3(OH)i6-4H2O.

[0163] Aspect 62. The pigment paste of any of aspects 42 to 61, wherein the pigment paste comprises an acid scavenger comprising hydrotalcite in an amount of 0.05 wt% to 2.0 wt%, based on the total weight of the paste.

[0164] Aspect 63. The pigment paste of any of aspects 42 to 62, wherein the pigment paste comprises a metal oxide comprising magnesium oxide.

[0165] Aspect 64. The pigment paste of any of aspects 42 to 63, wherein the pigment paste comprises a metal oxide comprising zinc oxide.

[0166] Aspect 65. The pigment paste of any of aspects 42 to 64, wherein the pigment paste comprises a metal oxide comprising lanthanum oxide.

[0167] Aspect 66. The pigment paste of any of aspects 42 to 65, wherein the pigment paste comprises a metal oxide comprising yttrium oxide.

[0168] Aspect 67. The pigment paste of any of aspects 42 to 66, wherein the pigment paste comprises a metal acetate comprising magnesium acetate.

[0169] Aspect 68. The pigment paste of any of aspects 42 to 67, wherein the pigment paste comprises a metal acetate comprising zinc acetate.

[0170] Aspect 69. The pigment paste of any of aspects 42 to 68, wherein the pigment paste comprises a metal acetate comprising calcium acetate.

[0171] Aspect 70. The pigment paste of any of aspects 42 to 69, wherein the pigment paste comprises a metal acetate comprising lanthanum acetate.

[0172] Aspect 71. The pigment paste of any of aspects 42 to 70, wherein the pigment paste comprises a metal acetate comprising magnesium acetate tetrahydrate.

[0173] Aspect 72. The pigment paste of any of aspects 42 to 71 , wherein the pigment paste comprises a metal acetate comprising magnesium acetate in an amount of 0.1 wt% to 3.0 wt%, based on total weight of the paste.

[0174] Aspect 73. An electrodepositable coating composition comprising: a. an electrodepositable binder; and b. any of the pigment pastes of aspects 42 to 72.

[0175] Aspect 74. The electrodepo sitable coating compositions of any of aspects 1 to41 and 73, wherein the concentration of phosphate ions is less than 5 ppm.

[0176] Aspect 75. The electrodepo sitable coating compositions of any of aspects 1 to41 and 73 to 74, wherein the concentration of phosphate ions is less than 3 ppm.

[0177] Aspect 76. The electrodepo sitable coating compositions of any of aspects 1 to41 and 73 to 75, wherein the concentration of phosphate ions is less than 1 ppm.

[0178] Aspect 77. The electrodepo sitable coating compositions of any of aspects 1 to41 and 73 to 76, wherein the total solids is 1% to 50% by weight, based on the total weight of the electrodepositable coating composition.

[0179] Aspect 78. The electrodepositable coating compositions of any of aspects 1 to 41 and 73 to77, wherein the total solids is 5% to 40% by weight, based on the total weight of the electrodepositable coating composition.

[0180] Aspect 79. The electrodepositable coating compositions of any of aspects 1 to 41 and 73 to 78, wherein the total solids may be 5% to 25% by weight, based on the total weight of the electrodepositable coating composition.

[0181] Aspect 80. Any of the electrodepositable coating compositions or pigment pastes of aspects 1 to 79, wherein the composition and / or paste is substantially free, essentially free, and / or completely free of zinc oxide.

[0182] Aspect 81. Any of the electrodepositable coating compositions or pigment pastes of aspects 1 to 80, wherein the composition and / or paste is substantially free, essentially free, and / or completely free of lanthanum oxide.

[0183] Aspect 82. Any of the electrodepositable coating compositions or pigment pastes of aspects 1 to 81, wherein the composition and / or paste is substantially free, essentially free, and / or completely free of yttrium oxide.

[0184] Aspect 83. Any of the electrodepositable coating compositions or pigment pastes of aspects 1 to 82, wherein the composition and / or paste is substantially free, essentially free, and / or completely free of magnesium oxide.

[0185] Aspect 84. A method for using the electrodepo siable coating compositions of any of aspects 1 to 41 and 73 to 83 to coat a substrate by electrodeposition of the coating composition onto at least a portion of the substrate.

[0186] Aspect 85. The method of aspect 84, wherein the substrate has been pretreated prior to electrodeposition.

[0187] Aspect 86. The method of any of aspects 84 to 85, wherein the substrate has been pretreated prior to electrodeposition with a non-metal phosphate pretreatment composition.

[0188] Aspect 87. A coated substrate prepared according to any of aspect 84 to 86.

[0189] Aspect 88. The substrate of aspect 87, wherein the substrate comprises metal.

[0190] Aspect 89. The substrate of aspect 87, wherein the metal comprises steel.

[0191] Aspect 90. The substrate of aspect 87, wherein the metal comprises aluminum.

[0192] Aspect 91. The substrate of aspect 90, wherein the aluminum comprises an aluminum alloy.

[0193] Aspect 92. The substrate of aspect 91, wherein the aluminum alloy is from the1XXX, 2XXX, 3XXX, 4XXX, 5XXX, 6XXX, or 7XXX series.

[0194] Aspect 93. The substrate of aspect 90, wherein the aluminum is a clad aluminum alloy.

[0195] Aspect 94. The substate of aspect 88, wherein the substrate comprises a multi- metal article.

[0196] Aspect 95. The substrate of any of aspects 87 to 94, wherein the coating layer deposited from the electrodepositable coating composition forms part of a coating stack.

[0197] Aspect 96. A vehicle comprising the substrate of any of aspects 87 to 95.

[0198] Aspect 97. A battery or battery component comprising the substrate of any of aspects 87 to 95.

[0199] Aspect 98. A vehicle comprising the battery of aspect 97.

[0200] The following examples are intended to illustrate the disclosure and should not be construed as limiting the disclosure in any way.EXAMPLESExample 1Resin System I

[0201] Preparation of Crosslinker I. A blocked polyisocyanate crosslinker, suitable for use in electrodepositable coating resins, was prepared in the following manner. Components 2-6 listed in Table 1, below, were mixed in a flask set up for total reflux with stirring under nitrogen. The mixture was heated to a temperature of 110°C, and Component 1 was added dropwise sothat the temperature increased due to the reaction exotherm and was maintained under 110°C. After the addition of Component 1 was complete, Component 7 was added to the heated reaction mixture. A temperature of 110°C was established in the reaction mixture and the reaction mixture held at temperature until no residual isocyanate was detected by IR spectroscopy. Components 8 and 9 were then added, and the reaction mixture was allowed to stir for 30 minutes and cooled to ambient temperature.Table 1. Components for the preparation of Crosslinker IPolymeric methylene diphenyl diisocyanate, available from Huntsman Corporation.2l-methoxy-2-propanol available from Dow.

[0202] Preparation of an Amine-Functionalized, Polyepoxide-Based Resin (Resin System I). An amine-functionalized, poly epoxide-based polymeric resin, suitable for use in formulating electrodepositable coating compositions, was prepared in the following manner. Components 1- 4 listed in Table 2, below, were combined in a flask set up for total reflux with stirring under nitrogen. The mixture was heated to a temperature of 130°C and allowed to exotherm (170°C maximum). A temperature of 145 °C was established in the reaction mixture and the reaction mixture was then held for 1.5 hours. Components 5-7 were then introduced into the reaction mixture and a temperature of 100°C was established in the reaction mixture. Components 8 and 9 were then added to the reaction mixture quickly and the reaction mixture was allowed to exotherm. A temperature of 110°C was established in the reaction mixture and the reactionmixture held for 1 hour. After the hold, the heating source was removed from the reaction mixture and Component 10 was added. The content of the flask was allowed to stir while cooling to room temperature. The resulting product had a solids content of 86.9% by weight.Table 2. Components for the preparation of Resin System I3Bisphenol A diglycicyl ether, available from Westlake, epoxy equivalent weight 186-190.Resin Dispersion I: Resin Dispersion for Example 1

[0203] Preparation of a Cationic, Polyetheramine-Functionalized, Polyepoxide-Based Resin (Resin Dispersion I). A cationic, polyetheramine-functionalized, polyepoxide-based polymeric resin, suitable for use in formulating electrodepo sitable coating compositions, was prepared in the following manner. Components 1-3 listed in Table 3, below, were combined in a flask set up for total reflux with stirring under nitrogen. The mixture was heated to a temperature of 130°C and mixed. Component 4 was added to the mixture and a temperature of 135°C was established and held for at least 1 hour until a target epoxy equivalent weight of 549 was achieved. Component 5 was then added to the mixture and a temperature of 100°C was established in the reaction mixture. Components 6 and 7 were then added to the reaction mixture and allowed to exotherm. A temperature of 95 °C was established in the reaction mixture and the mixture was stirred for 3 hours. The contents of the flask were then solubilized into pre-blendedComponents 8 and 9 and mixed for 30 minutes. Component 10 was then added over 30 minutes.The resulting Resin Dispersion I had a solids content of 45% by weight.Table 3. Components for the preparation of Resin Dispersion IPolypropylene oxide diamine, available from Huntsman.Resin Dispersion II: Resin Dispersion for Example 1

[0204] Preparation of a Cationic, Polyetheramine-Functionalized, Polyepoxide-Based Resin (Resin Dispersion II). A cationic, polyetheramine-functionalized, poly epoxide-based polymeric resin, suitable for use in formulating electrodepo sitable coating compositions, was prepared in the following manner. Components 1-3 listed in Table 4, below, were combined in a flask set up for total reflux with stirring under nitrogen. The mixture was heated to a temperature of 130°C and mixed. Component 4 was added to the mixture and a temperature of 135°C was established and held until a target epoxy equivalent weight of 1232 was achieved. The mixture was cooled to 95 °C and then Component 5 was added to the mixture and a temperature of 95 °C was held until the Gardner-Holdt viscosity of a sample of the resin diluted 50 / 50 in methoxy propanol was “HJ”. Components 6 and 7 were then added to the reaction mixture and allowed to mix until the Gardner-Holdt viscosity of a sample of the resin diluted 50 / 50 in methoxy propanol was “Q-”. The contents of the flask were then solubilized into pre-blended Components 8 and 9 and mixed for 30 minutes. Component 10 was then added over 30 minutes. The resulting Resin Dispersion II had a solids content of 36% by weight.Table 4. Components for the preparation of Resin Dispersion II'Aliphatic diepoxide having an epoxy equivalent weight of ~310-330available from the Dow Chemical Company.Polypropylene oxide diamine, available from Huntsman.3EPON 880, available from Westlake.Resin Dispersion III: Resin Dispersion for Example 1

[0205] Preparation of a Cationic, Poly etheramine- Functionalized, Polyepoxide-Based Resin (Resin Dispersion III). A cationic, polyetheramine-functionalized, polyepoxide-based polymeric resin, suitable for use in formulating electrodepo sitable coating compositions, was prepared in the following manner. Components 1-3 listed in Table 5, below, were combined in a flask set up for total reflux with stirring under nitrogen. The mixture was heated to a temperature of 130°C and mixed. Component 4 was added to the mixture and a temperature of 135°C was established and held until a target epoxy equivalent weight of 1360 was achieved. The mixture was cooled to 100°C and then Component 5 and 6 was added to the mixture. Component 7 was then added at 100°C to the reaction mixture and allowed to mix for 20 minutes. Component 8 was then added to the reaction mixture and allowed to mix until the Gardner-Holdt viscosity of a sample of the resin diluted 50 / 50 in methoxy propanol is “Q-”. 86% of the mixture’s contents from the flask were then solubilized into pre-blended Components 10 and 11 and mixed for 30 minutes at 60°C. Component 9 was then added and mixed for 30 minutes at 60°C. Heating was then removed and component 12 was added over 30 minutes. The resulting Resin Dispersion III had a solids content of 41% by weight.Resin Dispersion IV : Resin Dispersion for Example 1

[0206] Preparation of a Cationic, Amine-Functionalized, Polyepoxide-Based Resin (Resin Dispersion IV). A cationic, amine-functionalized, polyepoxide-based polymeric resin, suitable for use in formulating electrodepositable coating compositions, was prepared in the following manner. A pre -blended solution of Components 2 and 3 from Table 6 below were used to solubilize and disperse Resin System 1 by being added to component 1 over 5 minutes. The resulting dispersion was held for 1 hour at 60°C.Bismuth Catalyst Solution I: Catalyst Solution for Example 1

[0207] An aqueous bismuth methane sulfonate catalyst solution was prepared using the ingredients from Table 7 in the following manner: Component 1 was added to an Erlenmeyer flask with stirring, followed by the sequential introduction of Components 2 and 3. The contentof the flask was stirred for 3 hours at room temperature, and the resulting catalyst solution was then filtered through a Buchner funnel to remove any undissolved residue.Table 7. Components for the preparation of a catalyst solution770% solution in deionized water. All methane sulfonic acid was at this concentration unless indicated otherwise.85N Frit grade.Acid Scavenger Paste I: Paste for Example 1

[0208] A cationic, acid-scavenger containing paste, suitable for use in formulating electrodepositable coating compositions, was prepared in the following manner. Components 1 and 2 from Table 8 below were combined and mixed for 10 minutes in a stainless-steel beaker using constant agitation powered by a Fawcett air motor (Model 103 A) and a 1.5-inch Cowles blade. Component 3 was then added to the mixture and mixed for an additional 10 minutes. Components 4 and 5 were then added in quarter sized portions, alternating between adding component 4 and 5 until all the components were added. The paste was mixed until completely homogenous. Once homogenous, the paste was placed on a conventional media mill and ground until a Hegman above 7 was observed.Table 8. Components for the preparation of an Acid Scavenger Paste9Hydrotalcite commercially available from BASF.10Hydrous aluminosilicate commercially available from BASF.Electrodepositable Coating Compositions for Example 1

[0209] Control Formulation: An electrodepositable coating composition was prepared in the following manner. Components 2 and 4 listed in Table 9, below, were combined in a stainless- steel beaker and mixed by a Fawcett air motor (Model 103 A) using a 1.5-inch Cowles blade for 5 minutes stalling at 60°C. Components 1 and 3 were then added and the mixing speedwas increased to between 1500 - 2500 RPM. The mixture was allowed to mix for one hour after which the degree of the dispersion was determined by a Hegman gauge. To be adequately dispersed, a minimal reading of 5 had to be achieved.

[0210] For the dispersion step, a mixture of Components 5-8 was added to the pigment containing resinous mixture. A temperature of less than 60°C was established and the dispersion was mixed with a high-lift blade at between 500 - 1500 RPM for one hour. After dispersing, the dispersion was allowed to cool to ambient temperatures and Component 9 was added into the dispersed formulation and allowed to mix under ambient temperatures for one hour. To generate the electrocoat bath composition, the mixture was further diluted with Component 10 to 25% solids by weight.Table 9. Components for the preparation of a control electrodepo sitable coating composition

[0211] Formulation A.- An electrodepo sitable coating composition was prepared in the following manner. Components 2 and 4 listed in Table 10, below, were combined in a stainless- steel beaker and mixed by a Fawcett air motor (Model 103 A) using a 1.5-inch Cowles blade for 5 minutes starting at 60°C. Component 5 was then added to the mixture and allowed to mix for 15 minutes. Components 1 and 3 were then added and the mixing speed was increased to between 1500 - 2500 RPM. The mixture was allowed to mix for one hour after which the degree of the dispersion was determined by a Hegman gauge. To be adequately dispersed, a minimal reading of 5 had to be achieved.

[0212] For the dispersion step, a mixture of Components 6-9 was added to the pigment containing resinous mixture. A temperature of less than 60°C was established and the dispersion was mixed with a high-lift blade at between 500 - 1500 RPM for one hour. After dispersing, the dispersion was allowed to cool to ambient temperatures and Component 10 was added into the dispersed formulation and allowed to mix for one hour. To generate the electrocoat bath composition, the mixture was further diluted with Component 11 to 25% solids by weight.

[0213] Formulation B: An electrodepo sitable coating composition was prepared in the following manner. Components 2 and 4 listed in Table 11, below, were combined in a stainless- steel beaker and mixed by a Fawcett air motor (Model 103 A) using a 1.5-inch Cowles blade for 5 minutes starting at 60°C. Component 5 was then added to the mixture and allowed to mix for 15 minutes. Components 1 and 3 were then added and the mixing speed was increased to between 1500 - 2500 RPM. The mixture was allowed to mix for one hour after which the degree of the dispersion was determined by a Hegman gauge. To be adequately dispersed, a minimal reading of 5 had to be achieved.

[0214] For the dispersion step, a mixture of Components 6-9 was added to the pigment containing resinous mixture. A temperature of less than 60°C was established and the dispersion was mixed with a high-lift blade at between 500 - 1500 RPM for one hour. After dispersing, thedispersion was allowed to cool to ambient temperatures and Component 10 was added into the dispersed formulation and allowed to mix for one hour. To generate the electrocoat bath composition, the mixture was further diluted with Component 11 to 25% solids by weight.Table 11. Components for the preparation of an electrodepositable coating composition formulation B

[0215] Formulation C: An electrodepositable coating composition was prepared in the following manner. Component 1 listed in Table 12 was heated to 50°C while mixing and then component 2 was added. This mixture was allowed to mix for 1 hour before letting cool to ambient temperature. Component 3 was then added to complete the electrocoat bath preparation.

[0216] Evaluation of Cure Response: CRS panels pretreated with zinc phosphate (C700 item: 28630 available from ACT, Hillsdale, MI.) were cut in half to yield a 4” by 6” panel. Panels were fully submerged in the electrocoat baths and electrodeposition began. A rectifier (Xantrax Model XFR600-2, Elkhart, Indiana, or Sorensen XG 300-5.6, Ameteck, Berwyn,Pennsylvania), which was DC-power supplied, was used to apply the electrodepositable coating. This film thickness was deposited by using a voltage / temperature / current condition for two minutes. Exact coating conditions for each paint are found in Table 13. After panels were electrocoated, these panels were rinsed with deionized water and baked at 320°F (160°C) for 30 minutes in an electric oven (Despatch Model LFD-1-42). After baking, the panels were allowed to cool at ambient conditions for 20 minutes. Film thickness was measured using a Fischerscope MMS device purchased from Fischer Technology Inc. After measuring film thickness, cure was evaluated by double acetone rub testing. The baked panels were rubbed with an acetone soaked WYPAEE X80 disposable paper wipe manufactured by Kimberly-Clark. The rubs are counted as a double mb (one rub forward and mb backward constitutes a double mb). The panels are rated on a scale of 0-10 wherein the ratings correspond to the following scale: Cure Rating: 0 Breaks through to substrate in less than 10 mbs; 1 Breaks through to substrate in 10-19 mbs; 2 Breaks through to substrate in 20-29 rubs; 3 Breaks through to substrate in 30-39 mbs; 4 Breaks through to substrate in 40-49 mbs; 5 Breaks through to substrate in 50-99 rubs; 6 Heavy mar (100 mbs); 7 Mar (100 rubs); 8 Slight mar (100 mbs); 9 Trace mar (100 rubs); 10 No effect (100 rubs). Cure response ratings can be found in Table 13.Table 13. Comparisons of Cure Response

[0217] The data in Table 13 demonstrates a significant improvement to solvent resistance can be achieved when incorporating acid scavengers or magnesium acetate into the resin or pastes of bismuth catalyzed electrodepositable coatings with high levels of platelike pigments.Example 2Table 14. Preparation of Grind Resin A

[0218] Materials 1 and 2 were charged into a suitably equipped 3-liter round-bottomed flask. The mixture was heated to 130°C and Material 3 was added. The reaction mixture was held at 135°C until the epoxide equivalent weight of the mixture was 1232. Material 4 was then added and then the mixture was cooled to 95°C. Material 5 was added and the reaction held at 95°C until the Gardner-Holdt viscosity of a sample of the resin diluted 50 / 50 in methoxy propanol was “H-J”. A mixture of materials 6 and 7 was added and the mixture held until the Gardner-Holdt viscosity of a sample of the resin diluted 50 / 50 in methoxy propanol was “Q-”. 988.6g of this resin was poured into a mixture of Materials 9 and 10 and mixed for 30 minutes. Material 11 was then added and mixed well. The final aqueous dispersion had a measured solids content of 35.8%.Table 15: Preparation of blocked polyisocyanate curing agent (Crosslinker I)nPolymeric methylenediphenyl diisocyanate available from Covestro (NCO Eq Wt = 132).

[0219] A blocked polyisocyanate curing agent was prepared in the following manner.Components 2-5 were mixed in a flask set up for total reflux with stirring under nitrogen. Themixture was heated to a temperature of 30°C, and Component 1 was added slowly so that the temperature increased due to the reaction exotherm and was maintained below 100°C. After the addition of Component 1 was complete, the reaction mixture was held at 100°C until no residual isocyanate was detected by IR spectroscopy. Component 6 was then added, and the reaction mixture was allowed to stir for 30 minutes to yield the product.Table 16. Preparation of active hydrogen-containing, ionic salt group-containing film-forming polymer (Main Film-forming Polymer I)1372.7% by weight (in MIBK) of the diketimine reaction product of 1 equivalent of diethylenetriamine and 2 equivalents of MIBK.

[0220] An active hydrogen-containing, ionic salt group-containing film-forming polymer was prepared in the following manner. Components 1-5 were mixed in a flask set up for total reflux with stirring under nitrogen. The mixture was heated to a temperature of 130°C and allowed to exotherm (175°C maximum temperature). A temperature of 145°C was then established, and the reaction mixture was held for 2 hours. Component 6 was introduced while allowing the mixture to cool to 125 °C, followed by addition of Component 7. A temperature of 105°C was established, and Components 8-9 were added to the reaction mixture in rapid succession. The reaction mixture was allowed to exotherm, after which the mixture was held at 115°C for 1 hour to yield a Resin Synthesis Product (Component 10). A portion of the Resin Synthesis Product, as Component 10, was then poured into a pre-mixed solution of Components11-12 to form a resin dispersion, and the resin dispersion was mixed for 30 minutes. Component 13 was introduced over 30 minutes, and the dispersion was mixed for a further 30 minutes. Component 14 was then added, and the dispersion was mixed well. Free MIBK was subsequently removed from the dispersion by distillation under vacuum at a temperature of 60- 70°C, affording a product with a final solids content of 40.2%.Table 17, Preparation of Bismuth Containing Pigment Pastes A through K

[0221] Each of the pigment dispersion pastes was prepared by sequentially adding ingredients 1-3 under high shear agitation for 30 minutes. Then material 4 was added and mixed for 10 minutes. Following the mixing time, materials 5-8 were added and mixed for 20 minutes. Material 9 was then added. When the ingredients were thoroughly blended, the pigmentdispersion was transferred to a vertical sand mill and ground to a Hegman value of > 7.5. The resulting pastes had a pigment to binder ratio by mass of 2.0: 1.Table 18. Preparation of Electrodepo sitable Coating Composition D14Prepared by a process comprising mixing a cationic poly epoxideamine reaction product and a polyepoxide crosslinking agent similar to Example B as described in U S. Pat. No. 5,096,556.

[0222] The electrodepo sitable coating composition described in Table 18, charges 1 - 4 were added sequentially into a plastic container at room temperature under agitation with 10 minutes of stirring after each addition. The mixture was stirred lor at least 30 minutes at room temperature. Charge 5 was then added, and the paint was allowed to stir until uniform, a minimum of 30 minutes. Charge 6 was added, and the paint was allowed to stir for a minimum of 30 minutes until uniform. The resulting cationic electrodepositable paint compositions had a solids content of 20%, determined according to ASTM D2369-20, and a pigment to binder ratio of 0.15:1.0 by weight.Evaluation of Paste and Electrodepositable Coating Compositions

[0223] The paste and coatings compositions were prepared and evaluated in accordance with the test methods described below. The results are reported in Tables 19 and 20 below.

[0224] Production of an electrodeposited coating on a substrate: Coated panels were prepared from cold rolled steel panels, 4 x 12 x 0.032 inches, available from ACT Laboratories of Hillside, Michigan, pretreated with CHEMFOS C700 / DI (CHEMFOS C700 is a zinc phosphate immersion pretreatment composition available from PPG Industries, Inc.). The electrodepositable coating composition was electrodeposited onto said metal panel by immersing them into a stirring bath at 32 degrees centigrade and connecting the cathode of a direct current rectifier to the panel and connecting the rectifier's anode to stainless steel tubing used to circulate cooling water for bath temperature control. The voltage was increased from 0 to a maximum voltage over a period of 30 seconds and then held at that voltage for an additional 90 seconds.The voltage applied to each bath was determined by the voltage that provided a cured dry film thickness of 18 microns for all paints after heating to 175°C for 20 minutes in an electric oven (Despatch Industries, model LFD series).

[0225] Determination of Paste Stability: The viscosity of the prepared paste was measured within 1 hour of preparation to obtain an initial viscosity (Vi) measurement. The paste was then aged overnight (16 - 24 hours) at room temperature (20 - 23°C). The viscosity was measured again to obtain an aged viscosity (VA). Viscosity was measured on a Brookfield DV- III Ultra Rheometer using spindle #3 at 50 rpm at room temperature (20 - 23°C) and reported in centipoise. The viscosity increase was determined by the following equation: 100The paste stability was rated by the following scale: A: less than 50% Increase; B: 51 - 100% Increase; C: 101 - 500% Increase; D: Greater than 500% Increase.

[0226] Cure Evaluation of Electrodeposited Coatings: The electrodepositable coating compositions coated onto 4" X 6" x 0.032" cold rolled steel panels pretreated with CHEMFOS C700 / DI (CHEMFOS C700 is a zinc phosphate immersion pretreatment composition available from PPG Industries, Inc.) and available from ACT Laboratories of Hillside, Michigan.) by the methods set forth above were baked at 150°C or 175°C with a fixed bake time of 20 minutes using an electric oven (Despatch Industries, model LFD- series). Each of the panels had a dry film thickness between 0.7 to 0.9 mils (17 to 23 microns). The baked electrodeposited coatings were double rubbed with a cotton glove supplied by Uline Company placed over top of a nitrile glove soaked with excess amount of acetone for testing. The rubs are counted as a double rub (one rub forward and rub backward constitutes a double rub). The reported value is the number of double rubs performed before metal is observed from rubbing through the coating with a maximum of 100 rubs performed.

[0227] Roughness Evaluation of Electrodeposited Coatings: The coating texture of the panels electrocoated as described above was evaluated using a profilometer over a specified length of the panel, filtering the roughness profile according to ISO 4287-1997 3.1.6 using a Lc parameter of 2.5 mm and a Ls parameter of 8 pm before summarizing an Ra metric according to ISO 4287-1997 4,2,1, hereinafter referred to as “Ra”. The coating texture was evaluated using a Mitutoyo Surftest SJ-402 skidless stylus profilometer equipped with a 4 mN detector and a diamond stylus tip with a 90° cone and a 5 pm tip radius. The scan length, measuring speed, anddata sampling interval was 48 mm, 1 mm / s, and 5 pm, respectively. The raw data was first filtered to a roughness profile according to ISO 4287-1997 3.1.6 using a Lc parameter of 2.5 mm and an Ls parameter of 8 pm before summarizing an Ra metric according to ISO 4287-1997 4.2.1.Table 20. Properties of Electrodepo sitable Coating Composition D

[0228] The results show that the addition of the hydrotalcite to the paste improves paste stability while maintaining cure performance and smoothness of the coating.

[0229] Whereas particular examples of this disclosure have been described above for purposes of illustration, it will be evident to those skilled in the art that numerous variations of the details of the present disclosure may be made without departing from the disclosure as defined in the appended claims.

Claims

What is claimed is:

1. An electrodepositable coating composition comprising: a cationic salt group-containing film-forming polymer comprising active hydrogen functional groups; a blocked polyisocyanate curing agent; a bismuth catalyst; and an acid scavenger, a metal oxide, and / or a metal acetate, with the provisos that: the electrodepositable coating composition is substantially free, essentially free, or completely free of a dispersing acid comprising an oxyacid of phosphorus, the P:B of the composition is 0.2 or greater: 1 and when the acid scavenger comprises hydrotalcite, the hydrotalcite is substantially free of of divalent metals other than magnesium, and / or the hydrotalcite has more than one magnesium atom per molecule of hydrotalcite.

2. The electrodepositable coating composition of claim 1, wherein the bismuth catalyst comprises an at least partially solubilized bismuth catalyst.

3. The electrodepositable coating composition of claim 1 or 2, wherein the bismuth catalyst comprises bismuth methane sulphonate, bismuth ethane sulphonate, or a combination thereof.

4. The electrodepositable coating composition of any preceding claim, wherein the acid scavenger comprises a hydrotalcite.

5. The electrodepositable coating composition of any preceding claim, wherein the metal oxide comprises magnesium oxide, zinc oxide, lanthanum oxide, lanthanum acetate, and / or yttrium oxide.

6. The electrodepositable coating composition of any preceding claim, wherein the metal acetate comprises magnesium acetate, zinc acetate, calcium acetate, and / or lanthanum acetate.

7. The electrodepo sitable coating composition of any preceding claim, wherein the metal acetate comprises magnesium acetate.

8. The electrodepo sitable coating composition of any preceding claim, further comprising a plate-like pigment.

9. The electrodepo sitable coating composition of claim 8, wherein the plate-like pigment comprises kaolin clay.

10. A pigment paste for an electrodepositable coating composition comprising: a grind resin; and a pigment component comprising a plate-like pigment and an acid scavenger, a metal oxide and / or a metal acetate, wherein the plate-like pigment is present in an amount of at least 50% by weight, based on the total weight of pigment in the pigment component and the metal oxide does not comprise yttrium oxide.

11. The pigment paste of claim 10, further comprising a bismuth catalyst.

12. A pigment paste for an electrodepositable coating composition comprising: a cationic salt group- containing resin; a bismuth catalyst, and a pigment component comprising an acid scavenger, metal oxide, and / or metal acetate and when the acid scavenger comprises hydrotalcite, the hydrotalcite is substantially free of divalent metals other than magnesium, and / or the hydrotalcite has more than one magnesium atom per molecule of hydrotalcite.

13. The pigment paste of claim 12, further comprising a plate-like pigment.

14. The pigment paste of any of clams 10-13, wherein the paste comprises a bismuth catalyst and the bismuth metal from the catalyst is present in an amount of greater than 3% by weight, based on total solids weight.

15. The pigment paste of any of clams 10-14, wherein the paste comprises a bismuth catalyst comprising bismuth methane sulphonic acid.

16. The pigment paste of any of claims 10-15, wherein the paste comprises hydrotalcite having the formula Mg6A12CO3(OH)i6-4H2O.

17. The pigment paste of any of claims 10-16, wherein the pigment paste comprises a metal acetate comprising magnesium acetate.

18. An electrodepositable coating composition comprising: an electrodepositable binder; and the pigment paste of any of claims 10 to 17.

19. The electrodepositable coating composition of any of claims 1-9 and 18, wherein the electrodepositable coating composition has a concentration of phosphate ions of less than 5 ppm.

20. A method for using the electrodepositable coating composition of any of claims 1-9, and 18-19 to coat a substrate by electrodeposition of the coating composition onto at least a portion of the substrate.

21. The method of claim 20, wherein the substrate has been pretreated with a non-metal phosphate pretreatment composition prior to electrodeposition.

22. A coated substrate prepared according to any of claims 20-21.

23. A vehicle comprising the coated substrate of claim 22.

24. A battery or battery component comprising the coated substrate of claim 22.

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