Electrodepositable coating composition and method of coating a substrate

Abstract

The present disclosure relates to a cationically electrodepositable coating composition comprising: a film-forming polymer comprising cationic salt groups; a polymer comprising at least one phosphorylated group; and a curing agent. A method of coating a substrate and a coated substrate are also disclosed.

Description

Technical Field

[0001] The present disclosure relates to an electrodepositable coating composition, a coated substrate, and a method of coating a substrate. Background Art

[0002] As a coating application method, electrodeposition involves depositing a film-forming composition onto a conductive substrate under the influence of an applied electric potential. Compared to non-electrophoretic coating methods, electrodeposition is becoming increasingly popular in the coating industry due to its higher coating utilization, excellent corrosion resistance, and low environmental pollution. Summary of the Invention

[0003] The present disclosure provides a cationic electrodepositable coating composition comprising: an aromatic film-forming polymer containing a cationic salt group; an addition polymer comprising at least one phosphate group and optionally at least one hydroxyl functional group, wherein when the addition polymer comprises a (meth)acrylamide monomer, the addition polymer does not comprise a cationic or anionic salt group, and the addition polymer comprises less than 60 wt. % of structural units comprising residues of hydroxyl-functional (meth)acrylate monomers and / or hydroxyl-functional (meth)acrylamide monomers, based on the total weight of the addition polymer; and a curing agent.

[0004] The present disclosure also provides a cationic electrodepositable coating composition comprising: an aromatic film-forming polymer containing a cationic salt group; an addition polymer comprising a polymerization product of a monomer composition comprising: (a) C1-C 18 (b) a phosphoric acid-containing monomer, wherein when the addition polymer comprises a (meth)acrylamide monomer, the addition polymer does not comprise a cationic or anionic salt group and the addition polymer comprises less than 60 wt. % of structural units comprising residues of hydroxy-functional (meth)acrylate monomers and / or hydroxy-functional (meth)acrylamide monomers, based on the total weight of the addition polymer; and a curing agent.

[0005] The present disclosure further provides a cationic electrodepositable coating composition comprising: an aromatic film-forming polymer containing a cationic salt group; a phosphated epoxy resin; and a curing agent.

[0006] The present disclosure also provides a cationic electrodepositable coating composition comprising: a cationic salt group-containing aromatic film-forming polymer; a polymer comprising at least one phosphated group and optionally at least one hydroxyl functional group, wherein when the polymer comprises a (meth)acrylamide monomer, the polymer does not comprise a cationic or anionic salt group, and the polymer comprises less than 60 weight percent of constitutional units comprising residues of a hydroxyl functional (meth)acrylate monomer and / or a hydroxyl functional (meth)acrylamide monomer, based on the total weight of the polymer; a curing agent; and a pigment, wherein the pigment to binder ratio is greater than 0.5: 1, such as at least 0.60: 1, such as at least 0.70: 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.

[0007] The present disclosure further provides a cationic electrodepositable coating composition comprising: a cationic salt group-containing aromatic film-forming polymer; a polymer comprising at least one phosphated group and optionally at least one hydroxyl functional group, wherein when the polymer comprises a (meth)acrylamide monomer, the polymer does not comprise a cationic or anionic salt group, and the polymer comprises less than 60 weight percent of constitutional units comprising residues of a hydroxyl functional (meth)acrylate monomer and / or a hydroxyl functional (meth)acrylamide monomer, based on the total weight of the polymer; a curing agent; and a pigment, wherein the pigment to binder ratio is greater than 0.67: 1, such as at least 0.70: 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.

[0008] The present disclosure also provides a cationic electrodepositable coating composition comprising: a cationic salt group-containing aromatic film-forming polymer; a polymer comprising at least one phosphated group and optionally at least one hydroxyl functional group, wherein when the polymer comprises a (meth)acrylamide monomer, the polymer does not comprise a cationic salt group; a curing agent; and an inorganic platelet pigment, wherein the inorganic platelet pigment to binder ratio is at least 0.4: 1, such as at least 0.5: 1, such as at least 0.60: 1, such as at least 0.70: 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.

[0009] The present disclosure further provides a method for coating a metal substrate, comprising: (1) immersing the surface of the metal substrate to be coated into a cationic electrodepositable coating composition, the cationic electrodepositable coating composition comprising: (a) a film-forming polymer containing cationic salt groups; (b) a curing agent; and (c) a phosphate ion source or a polymer containing at least one phosphated group, wherein the metal substrate serves as a cathode electrically connected to an anode immersed in the cationic electrodepositable coating composition; (2) allowing the immersed metal substrate to remain in the cationic electrodepositable coating composition for a certain period of time, thereby forming a metal phosphate layer on at least a portion of the surface of the metal substrate; and (3) applying a direct current between the cathode and the anode, thereby depositing a coating formed from the cationic electrodepositable coating composition on the surface of the metal substrate.

[0010] The present disclosure also provides a method for coating a metal substrate, comprising: (1) immersing the surface of the metal substrate to be coated in a cationic electrodepositable coating composition, the cationic electrodepositable coating composition comprising: (a) a film-forming polymer containing cationic salt groups; (b) a curing agent; and (c) a phosphate ion source or a polymer containing at least one phosphated group, wherein the metal substrate serves as an electrode electrically connected to a counter electrode immersed in the cationic electrodepositable coating composition; (2) applying a direct current between the electrode and the counter electrode, wherein the electrode serves as an anode and the counter electrode serves as a cathode, thereby forming a metal phosphate layer on at least a portion of the surface of the metal substrate; and (3) applying a direct current between the electrode and the counter electrode, wherein the polarity is reversed and the electrode serves as a cathode and the counter electrode serves as an anode, thereby depositing a coating formed from the cationic electrodepositable coating composition on the surface of the metal substrate.

[0011] The present disclosure further provides a method for coating a metal substrate, comprising: (1) immersing the surface of the metal substrate to be coated into a cationic electrodepositable coating composition, the cationic electrodepositable coating composition comprising: (a) a film-forming polymer containing cationic salt groups; (b) a curing agent; and (c) a phosphate ion source or a polymer containing at least one phosphated group, wherein the metal substrate serves as an electrode electrically connected to a counter electrode immersed in the cationic electrodepositable coating composition; and (2) applying a direct current between the electrode and the counter electrode, wherein the electrode serves as a cathode and the counter electrode serves as an anode, thereby depositing a coating formed from the cationic electrodepositable coating composition on the surface of the metal substrate; wherein the metal substrate has not been treated with a pretreatment composition prior to immersion in the cationic electrodepositable coating composition. DETAILED DESCRIPTION

[0012] The present disclosure relates to a cationic electrodepositable coating composition comprising: a film-forming polymer containing a cationic salt group; a polymer containing at least one phosphate group; and a curing agent.

[0013] As used herein, the term "electrodepositable coating composition" refers to a composition capable of being deposited onto a conductive substrate under the influence of an electric potential applied between two electrodes immersed in the electrodepositable coating composition, wherein one of the electrodes is the substrate to be coated.

[0014] The cationic electrodepositable coating composition includes a polymer comprising at least one phosphorylated group. The polymer is not limited. Non-limiting examples of polymers include addition polymers comprising at least one phosphorylated group, phosphated epoxy resins, and other polymers comprising at least one phosphorylated group.

[0015] As used herein, the terms "phosphorylated group" and "phosphate group" refer to a phosphate group attached to a polymer. As used herein, "phosphate" refers to a group derived from phosphoric acid having the general chemical formula [PO4] 3- , [HPO4] 2- and / or [H2PO4] - Although reference is made herein to "phosphate" ions, other derivatives of phosphoric acid derivatives are also within the scope of this disclosure. Therefore, unless otherwise indicated, phosphate ions may refer to compounds having the general chemical formula [RPO3] 2- and / or [RHPO3] 1- of a phosphonate anion derived from a phosphonic acid, and a phosphinate anion derived from a phosphinic acid.

[0016] The polymer may have a phosphoric acid equivalent weight of at least 0.01 milliequivalents, such as at least 0.05 milliequivalents, such as at least 0.1 milliequivalents, such as at least 1 milliequivalents, such as at least 2 milliequivalents, such as at least 4 milliequivalents per gram of polymer. The polymer may have a phosphoric acid equivalent weight of no more than 10 milliequivalents, such as no more than 7 milliequivalents, such as no more than 5 milliequivalents, such as no more than 3 milliequivalents, such as no more than 2 milliequivalents, such as no more than 1 milliequivalent per gram of polymer. The polymer may have a molecular weight per gram of polymer of 0.01 to 10 milliequivalents, such as 0.01 to 7 milliequivalents, such as 0.01 to 5 milliequivalents, such as 0.01 to 3 milliequivalents, such as 0.01 to 2 milliequivalents, such as 0.01 to 1 milliequivalents, such as 0.05 to 10 milliequivalents, such as 0.05 to 7 milliequivalents, such as 0.05 to 5 milliequivalents, such as 0.05 to 3 milliequivalents, such as 0.05 to 2 milliequivalents, such as 0.05 to 1 milliequivalents, such as 0.1 to 10 milliequivalents, such as 0. The phosphoric acid equivalent weight is 0.1 to 7 milliequivalents, such as 0.1 to 5 milliequivalents, such as 0.1 to 3 milliequivalents, such as 0.1 to 2 milliequivalents, such as 0.1 to 1 milliequivalents, such as 1 to 10 milliequivalents, such as 1 to 7 milliequivalents, such as 1 to 5 milliequivalents, such as 1 to 3 milliequivalents, such as 1 to 2 milliequivalents, such as 2 to 10 milliequivalents, such as 2 to 7 milliequivalents, such as 2 to 5 milliequivalents, such as 2 to 3 milliequivalents, such as 4 to 10 milliequivalents, such as 4 to 7 milliequivalents, such as 4 to 5 milliequivalents. The phosphoric acid equivalent weight can be determined by dividing the total weight of the polymer by the total number of phosphate groups present in the polymer.

[0017] The polymer comprising at least one phosphorylated group may include an addition polymer. As used herein, the term "addition polymer" refers to a polymer product formed by a polymerization reaction of the monomers constituting the monomer composition to form a polymer. After the monomers of the monomer composition are polymerized, the addition polymer comprises a structural unit corresponding to the residue of each polymerized monomer. As used herein, the term "residue of..." when referring to the composition of a polymer refers to a single molecular unit (i.e., structural unit) of the polymer that originates from the incorporation (i.e., reaction) of a monomer during polymerization. An addition polymer is formed by polymerizing a monomer composition comprising ethylenically unsaturated monomers.

[0018] The monomer composition comprises a phosphoric acid functional monomer. The phosphoric acid group may comprise a phosphoric acid group, a phosphinic acid group or a combination thereof, and salts thereof. The phosphoric acid functional ethylenically unsaturated monomer may be a dihydrogen phosphate ester of an alcohol, wherein the alcohol contains or is substituted with a polymerizable vinyl or olefinic group. Suitable phosphoric acid functional ethylenically unsaturated monomers may comprise phosphoalkyl (meth)acrylates, such as phosphoethyl (meth)acrylate, phosphopropyl (meth)acrylate, phosphobutyl (meth)acrylate, salts of phosphoalkyl (meth)acrylates, and mixtures thereof; CH2═C(R)—C(O)—O—(Rp O) n —P(O)(OH)2, where R═H or CH3 and R p =alkyl, n is 1 to 20, such as SIPOMER PAM-100, SIPOMER PAM-200, SIPOMER PAM-300 and SIPOMER PAM-4000, all available from Solvay; phosphoalkoxy (meth) acrylates, such as ethylene glycol phosphate (meth) acrylate, diethylene glycol phosphate (meth) acrylate, triethylene glycol phosphate (meth) acrylate, propylene glycol phosphate (meth) acrylate, dipropylene glycol phosphate (meth) acrylate, tripropylene glycol phosphate (meth) acrylate, their salts and mixtures thereof. Based on the total weight of the monomer composition, the phosphoric acid functional monomer can be present in the monomer composition in an amount of at least 0.1 wt%, such as at least 1 wt%, such as at least 2 wt%. Based on the total weight of the monomer composition, the phosphoric acid functional monomer can be present in the monomer composition in an amount of not more than 20 wt%, such as not more than 10 wt%, such as not more than 8 wt%. The phosphoric acid functional monomer may be present in the monomer composition in an amount of 0.1 wt % to 20 wt %, such as 0.1 wt % to 10 wt %, such as 0.1 wt % to 8 wt %, such as 1 wt % to 20 wt %, such as 1 wt % to 10 wt %, such as 1 wt % to 8 wt %, such as 2 wt % to 20 wt %, such as 2 wt % to 10 wt %, such as 2 wt % to 8 wt %, based on the total weight of the monomer composition.

[0019] The monomer composition and the resulting addition polymer may also contain at least one other ethylenically unsaturated monomer or residue thereof. For example, the monomer composition and the resulting addition polymer may also contain C1-C 18 Alkyl (meth)acrylate monomers; hydroxyl functional (meth)acrylate monomers; vinyl aromatic compounds; monomers containing two or more ethylenically unsaturated groups per molecule; (meth)acrylamide monomers; monoalkyl (meth)acrylamide monomers; dialkyl (meth)acrylamide monomers; and / or hydroxyl functional (meth)acrylamide monomers.

[0020] As used herein, the terms "(meth)acrylate" or "(meth)acrylamide" encompass both acrylate and methacrylate, or acrylamide and methacrylamide, respectively.

[0021] The hydroxyl functional (meth) acrylate may include hydroxyalkyl (meth) acrylates, such as, for example, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, and the like, and combinations thereof. Based on the total weight of the monomer composition, the hydroxyl functional (meth) acrylate may be present in the monomer composition in an amount of at least 1 wt %, such as at least 5 wt %, such as at least 10 wt %, such as at least 20 wt %, such as at least 30 wt %. Based on the total weight of the monomer composition, the hydroxyl functional (meth) acrylate may be present in the monomer composition in an amount of less than 60 wt %, such as no more than 50 wt %, such as no more than 40 wt %. The hydroxyl functional (meth)acrylate may be present in the monomer composition in an amount of 1 wt % to less than 60 wt %, such as 1 wt % to 55 wt %, such as 1 wt % to 50 wt %, such as 1 wt % to 40 wt %, such as 5 wt % to less than 60 wt %, such as 5 wt % to 55 wt %, such as 5 wt % to 50 wt %, such as 5 wt % to 40 wt %, such as 10 wt % to less than 60 wt %, such as 10 wt % to 55 wt %, such as 10 wt % to 50 wt %, such as 10 wt % to 40 wt %, such as 20 wt % to less than 60 wt %, such as 20 wt % to 55 wt %, such as 20 wt % to 50 wt %, such as 20 wt % to 40 wt %, such as 30 wt % to less than 60 wt %, such as 30 wt % to 55 wt %, such as 30 wt % to 50 wt %, such as 30 wt % to 40 wt %.

[0022] The hydroxyl functional (meth) acrylamide monomer may include hydroxyalkyl (meth) acrylamides, such as, for example, hydroxymethyl (meth) acrylamide, hydroxyethyl (meth) acrylamide, hydroxypropyl (meth) acrylamide, 2-hydroxypropyl (meth) acrylamide, hydroxybutyl (meth) acrylamide, hydroxypentyl (meth) acrylamide, and the like, and combinations thereof. Based on the total weight of the monomer composition, the hydroxyl functional (meth) acrylamide monomer may be present in the monomer composition in an amount of at least 1 wt %, such as at least 5 wt %, such as at least 10 wt %, such as at least 20 wt %, such as at least 30 wt %. Based on the total weight of the monomer composition, the hydroxyl functional (meth) acrylamide monomer may be present in the monomer composition in an amount of less than 60 wt %, such as no more than 50 wt %, such as no more than 40 wt %. The hydroxyl-functional (meth)acrylamide monomer can be present in the monomer composition in an amount of 1 wt % to less than 60 wt %, such as 1 wt % to 55 wt %, such as 1 wt % to 50 wt %, such as 1 wt % to 40 wt %, such as 5 wt % to less than 60 wt %, such as 5 wt % to 55 wt %, such as 5 wt % to 50 wt %, such as 5 wt % to 40 wt %, such as 10 wt % to less than 60 wt %, such as 10 wt % to 55 wt %, such as 10 wt % to 50 wt %, such as 10 wt % to 40 wt %, such as 20 wt % to less than 60 wt %, such as 20 wt % to 55 wt %, such as 20 wt % to 50 wt %, such as 20 wt % to 40 wt %, such as 30 wt % to less than 60 wt %, such as 30 wt % to 55 wt %, such as 30 wt % to 50 wt %, such as 30 wt % to 40 wt %.

[0023] In examples, the addition polymer can comprise less than 60 wt% of structural units comprising residues of hydroxy-functional (meth)acrylate monomers and / or hydroxy-functional (meth)acrylamide monomers, based on the total weight of the addition polymer.

[0024] When hydroxyl-functional (meth)acrylate monomers and / or hydroxyl-functional (meth)acrylamide monomers are present, the addition polymer comprises hydroxyl functional groups. The addition polymer may have a hydroxyl value of at least 1, such as at least 10 mg KOH / g, such as at least 20 mg KOH / g, such as at least 50 mg KOH / g, such as at least 100 mg KOH / g. The addition polymer may have a hydroxyl value of no more than 500 mg KOH / g, such as no more than 300 mg KOH / g, such as no more than 200 mg KOH / g. The addition polymer may have a carbon mass of 1 mg KOH / g to 500 mg KOH / g, such as 1 mg KOH / g to 300 mg KOH / g, such as 1 mg KOH / g to 200 mg KOH / g, such as 10 mg KOH / g to 500 mg KOH / g, such as 10 mg KOH / g to 300 mg KOH / g, such as 10 mg KOH / g to 200 mg KOH / g, such as 20 mg KOH / g to 500 mg KOH / g, such as 20 mg KOH / g to 300 mg KOH / g, such as 20 mg KOH / g to 200 mg KOH / g, such as 50 mg KOH / g to 500 mg KOH / g, such as 50 mg KOH / g to 300 mg KOH / g, such as 50 mg KOH / g to 200 mg KOH / g, such as 100 mg KOH / g to 500 mg KOH / g, such as 100 mg KOH / g. A hydroxyl value of from 100 mg KOH / g to 300 mg KOH / g, such as from 100 mg KOH / g to 200 mg KOH / g. As used herein, the term "hydroxyl value" generally refers to the number of milligrams of potassium hydroxide (KOH) required to neutralize the acetic acid absorbed during the acetylation of one gram of a chemical substance containing free hydroxyl groups, and is determined herein by theoretical calculation of the number of free hydroxyl groups theoretically present in one gram of addition polymer.

[0025] Suitable C1-C 18 Examples of alkyl (meth)acrylates include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, isodecyl (meth)acrylate, stearyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobornyl (meth)acrylate, tert-butyl (meth)acrylate, and the like. Based on the total weight of the monomer composition, C1-C 18 The alkyl (meth)acrylate may be present in the monomer composition in an amount of at least 30 wt %, such as at least 40 wt %, such as at least 50 wt %, such as at least 60 wt %, such as at least 70 wt %. Based on the total weight of the monomer composition, the C1-C 18The alkyl (meth)acrylate may be present in the monomer composition in an amount of no more than 90 wt %, such as no more than 80 wt %, such as no more than 70 wt %, such as no more than 60 wt %. Based on the total weight of the monomer composition, the C1-C 18 The alkyl (meth)acrylate may be present in the monomer composition in an amount of 30 to 90 wt %, such as 30 to 80 wt %, such as 30 to 70 wt %, such as 30 to 60 wt %, such as 40 to 90 wt %, such as 40 to 80 wt %, such as 40 to 70 wt %, such as 40 to 60 wt %, such as 50 to 90 wt %, such as 50 to 80 wt %, such as 50 to 70 wt %, such as 50 to 60 wt %, such as 60 to 90 wt %, such as 60 to 80 wt %, such as 60 to 70 wt %, such as 70 to 90 wt %, such as 70 to 80 wt %.

[0026] Non-limiting examples of suitable vinyl aromatic compounds include styrene, α-methylstyrene, α-chloromethylstyrene and / or vinyltoluene. Based on the total weight of the monomer composition, the vinyl aromatic compound can be present in the monomer composition in an amount of at least 0.5 wt %, such as at least 1 wt %, such as at least 5 wt %, such as at least 10 wt %. Based on the total weight of the monomer composition, the vinyl aromatic compound can be present in the monomer composition in an amount of no more than 40 wt %, such as no more than 30 wt %, such as no more than 20 wt %, such as no more than 15 wt %, such as no more than 10 wt %. The vinyl aromatic compound may be present in the monomer composition in an amount of 0.5 wt % to 40 wt %, such as 0.5 wt % to 30 wt %, such as 0.5 wt % to 20 wt %, such as 0.5 wt % to 15 wt %, such as 0.5 wt % to 10 wt %, such as 1 wt % to 40 wt %, such as 1 wt % to 30 wt %, such as 1 wt % to 20 wt %, such as 1 wt % to 15 wt %, such as 1 wt % to 10 wt %, such as 5 wt % to 40 wt %, such as 5 wt % to 30 wt %, such as 5 wt % to 20 wt %, such as 5 wt % to 15 wt %, such as 5 wt % to 10 wt %, such as 10 wt % to 40 wt %, such as 10 wt % to 30 wt %, such as 10 wt % to 20 wt %, such as 10 wt % to 15 wt %.

[0027] Each molecule has the example of the suitable monomer of two ethylenically unsaturated groups and comprises ethylene glycol dimethacrylate, allyl methacrylate, hexanediol diacrylate, methacrylic anhydride, tetraethylene glycol diacrylate and / or tripropylene glycol diacrylate. Each molecule has the example of the monomer of three or more ethylenically unsaturated groups and comprises ethoxylated trimethylolpropane triacrylate with 0 to 20 ethoxy units, [ethoxylated] trimethylolpropane trimethacrylate with 0 to 20 ethoxy units, di-pentaerythritol triacrylate, pentaerythritol tetraacrylate and / or di-pentaerythritol pentaacrylate.Based on the gross weight of monomer composition, each molecule comprises the monomer of two or more ethylenically unsaturated groups and can be present in the monomer composition in an amount of at least 0.1 % by weight, such as at least 1 % by weight, such as at least 3 % by weight, such as at least 5 % by weight. Based on the gross weight of the monomer composition, the monomer containing two or more ethylenically unsaturated groups per molecule can be present in the electrodepositable coating composition in an amount of no more than 10 wt %, such as no more than 5 wt %, such as no more than 3 wt %. Based on the gross weight of the monomer composition, the monomer containing two or more ethylenically unsaturated groups per molecule can be present in the monomer composition in an amount of 0.1 wt % to 10 wt %, such as 0.1 wt % to 5 wt %, such as 0.1 wt % to 3 wt %, such as 1 wt % to 10 wt %, such as 1 wt % to 5 wt %, such as 1 wt % to 3 wt %, such as 3 wt % to 10 wt %, such as 3 wt % to 5 wt %, such as 5 wt % to 10 wt %.

[0028] Examples of suitable alkyl (meth) acrylamide monomers include C1-C 18alkyl(meth)acrylamide monomers such as, but not limited to, methyl (meth)acrylamide, ethyl (meth)acrylamide, butyl (meth)acrylamide, hexyl (meth)acrylamide, octyl (meth)acrylamide, isodecyl (meth)acrylamide, stearyl (meth)acrylamide, 2-ethylhexyl (meth)acrylamide, isobornyl (meth)acrylamide, t-butyl (meth)acrylamide, and the like. The alkyl(meth)acrylamide monomers can be present in the monomer composition in an amount of at least 30 wt.%, such as at least 40 wt.%, such as at least 50 wt.%, such as at least 60 wt.%, such as at least 70 wt.%, based on the total weight of the monomer composition. The alkyl(meth)acrylamide monomers can be present in the monomer composition in an amount of not more than 90 wt.%, such as not more than 80 wt.%, such as not more than 70 wt.%, such as not more than 60 wt.%, based on the total weight of the monomer composition. The alkyl(meth)acrylamide monomers can be present in the monomer composition in an amount of 30 wt.% to 90 wt.%, such as 30 wt.% to 80 wt.%, such as 30 wt.% to 70 wt.%, such as 30 wt.% to 60 wt.%, such as 40 wt.% to 90 wt.%, such as 40 wt.% to 80 wt.%, such as 40 wt.% to 70 wt.%, such as 40 wt.% to 60 wt.%, such as 50 wt.% to 90 wt.%, such as 50 wt.% to 80 wt.%, such as 50 wt.% to 70 wt.%, such as 50 wt.% to 60 wt.%, such as 60 wt.% to 90 wt.%, such as 60 wt.% to 80 wt.%, such as 60 wt.% to 70 wt.%, such as 70 wt.% to 90 wt.%, such as 70 wt.% to 80 wt.%, based on the total weight of the monomer composition.

[0029] Monomer composition optionally can comprise the monomer that each molecule comprises two or more ethylenically unsaturated groups.The monomer that each molecule comprises two or more ethylenically unsaturated groups can comprise the monomer that each molecule comprises two ethylenically unsaturated groups.The example that each molecule has the suitable monomer of two ethylenically unsaturated groups comprises ethylene glycol dimethacrylate, allyl methacrylate, hexanediol diacrylate, methacrylic anhydride, tetraethylene glycol diacrylate and / or tripropylene glycol diacrylate.The example that each molecule has the monomer of three or more ethylenically unsaturated groups comprises the ethoxylated trimethylolpropane triacrylate with 0 to 20 ethoxy units, [ethoxylation] trimethylolpropane trimethacrylate with 0 to 20 ethoxy units, di-pentaerythritol triacrylate, pentaerythritol tetraacrylate and / or di-pentaerythritol pentaacrylate. Based on the gross weight of monomer composition, the monomer that each molecule comprises two or more ethylenically unsaturated groups can at least 0.1 % by weight, such as at least 1 % by weight, such as at least 3 % by weight, such as the amount of at least 5 % by weight is present in the monomer composition.Based on the gross weight of monomer composition, the monomer that each molecule comprises two or more ethylenically unsaturated groups can be no more than 10 % by weight, such as being no more than 5 % by weight, such as the amount of being no more than 3 % by weight and be present in the coating composition that can be electrodeposited ...0.1 % by weight to 10 % by weight, such as 0.1 % by weight to 5 % by weight, such as 0.1 % by weight to 3 % by weight, such as 1 % by weight to 10 % by weight, such as 1 % by weight to 5 % by weight, such as 1 % by weight to 3 % by weight, such as 3 % by weight to 10 % by weight, such as 3 % by weight to 5 % by weight, such as 5 % by weight to 10 % by weight and be present in the monomer composition.

[0030] Addition polymers can be prepared by polymerizing an ethylenically unsaturated polymerizable monomer composition in a dispersion medium comprising water by techniques well known in the art. For example, the monomer composition can be dissolved or dispersed in water and subjected to addition polymerization conditions by heating in the presence of a free radical initiator. The monomer composition can optionally include a surfactant to assist in dispersing the monomer composition, and the surfactant can be a reactive surfactant or a non-reactive surfactant. Alternatively, the monomer composition can be substantially free of, essentially free of, or completely free of reactive and / or non-reactive surfactants. The time and temperature of the polymerization will depend on each other, the selected ingredients, and in some cases, the scale of the reaction. The polymerization can be carried out at, for example, 40° C. to 100° C. for 2 to 20 hours. The free radical initiator used for the polymerization can be selected from any free radical initiator used in aqueous latex polymerization techniques, including redox pair initiators, peroxides, hydroperoxides, peroxydicarbonates, azo compounds, and the like.

[0031] Addition polymers can be prepared in organic solutions by techniques well known in the art. For example, addition polymers can be prepared by conventional free radical-induced solution polymerization techniques, wherein the monomer composition is dissolved in a solvent or solvent mixture and polymerized in the presence of a free radical initiator. Examples of suitable solvents that can be used for organic solution polymerization include alcohols such as ethanol, tert-butyl alcohol and tert-amyl alcohol, tert-butyl alcohol and tert-amyl alcohol; ketones such as acetone, methyl ethyl ketone; and ethers such as dimethyl ether of ethylene glycol. Examples of suitable free radical initiators include free radical initiators soluble in a mixture of monomers, such as azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), azobis-(α, γ-dimethylvaleronitrile), tert-butyl perbenzoate, tert-butyl peracetate, benzoyl peroxide and di-tert-butyl peroxide. Based on the gross weight of the monomer composition, the free radical initiator can be present in an amount of 0.01 wt % to 6 wt %, such as 1.0 wt % to 4.0 wt %, such as 2.0 wt % to 3.5 wt %. In an example, the solvent can be first heated to reflux, and the mixture of the monomer composition and the free radical initiator can be slowly added to the refluxing solvent. The reaction mixture can be maintained at the polymerization temperature to reduce the free monomer content to less than 1.0 wt %, such as less than 0.5 wt %, based on the total weight of the monomer composition.

[0032] The ionic salt groups in the addition polymer, if present, can be formed by at least partially neutralizing the basic or acidic groups present in the acrylic polymer with an acid or base, respectively. The ionic groups in the polymer can be charge-neutralized by a counterion. The ionic groups and the charge-neutralizing counterion can together form salt groups, such that the addition polymer can include an acrylic polymer containing ionic salt groups.

[0033] Alternatively, the addition polymer does not comprise cationic or anionic salt groups. For example, when the addition polymer comprises a (meth)acrylamide monomer, the addition polymer may not comprise cationic and / or anionic salt groups.

[0034] The addition polymer may be substantially free, essentially free, or completely free of structural units comprising residues of vinyl alcohol. As used herein, an addition polymer is “substantially free” of structural units comprising residues of vinyl alcohol if such structural units, if any, are present in the addition polymer in an amount of less than 3% by weight, based on the total weight of the addition polymer. As used herein, an addition polymer is “essentially free” of structural units comprising residues of vinyl alcohol if such structural units, if any, are present in the addition polymer in an amount of less than 1% by weight, based on the total weight of the addition polymer. As used herein, an acrylic polymer is “completely free” of structural units comprising residues of vinyl alcohol if such structural units are not present in the addition polymer, i.e., 0% by weight. As used herein, “vinyl alcohol” refers to both vinyl alcohol monomer and vinyl esters that are hydrolyzed after polymerization to convert the esters into hydroxyl groups.

[0035] The addition polymer may be substantially free, essentially free, or completely free of structural units comprising the residue of a nitrogen-containing monomer. As used herein, an addition polymer is “substantially free” of structural units comprising the residue of a nitrogen-containing monomer if the structural units comprising the residue of a nitrogen-containing monomer, if any, are present in the addition polymer in an amount of less than 3% by weight, based on the total weight of the addition polymer. As used herein, an addition polymer is “essentially free” of structural units comprising the residue of a nitrogen-containing monomer if the structural units comprising the residue of a nitrogen-containing monomer, if any, are present in the addition polymer in an amount of less than 1% by weight, based on the total weight of the addition polymer. As used herein, an addition polymer is “completely free” of structural units comprising the residue of a nitrogen-containing monomer if the structural units comprising the residue of a nitrogen-containing monomer are not present in the addition polymer, i.e., 0% by weight.

[0036] The addition polymer may be substantially free, essentially free, or completely free of structural units comprising residues of dispersants. As used herein, an addition polymer is "substantially free" of structural units comprising residues of a polymeric dispersant if structural units comprising residues of a polymeric dispersant, if any, are present in the addition polymer in an amount of less than 15% by weight, based on the total weight of the addition polymer. As used herein, an addition polymer is "essentially free" of structural units comprising residues of a polymeric dispersant if structural units comprising residues of a polymeric dispersant, if any, are present in the addition polymer in an amount of less than 5% by weight, based on the total weight of the addition polymer. As used herein, an addition polymer is "completely free" of structural units comprising residues of a polymeric dispersant if structural units comprising residues of a polymeric dispersant are not present in the addition polymer, i.e., 0% by weight.

[0037] The addition polymer may be substantially free, essentially free, or completely free of structural units comprising the residues of diene monomers. As used herein, an addition polymer is “substantially free” of structural units comprising the residues of diene monomers if such structural units, if any, are present in the addition polymer in an amount of less than 2% by weight, based on the total weight of the addition polymer. As used herein, an addition polymer is “essentially free” of structural units comprising the residues of diene monomers if such structural units, if any, are present in the addition polymer in an amount of less than 0.1% by weight, based on the total weight of the addition polymer. As used herein, an addition polymer is “completely free” of structural units comprising the residues of diene monomers if such structural units are not present in the addition polymer, i.e., 0.0% by weight.

[0038] The addition polymer may be substantially free, essentially free, or completely free of structural units comprising the residue of isobutylene monomer. As used herein, an addition polymer is “substantially free” of structural units comprising the residue of isobutylene monomer if such structural units, if any, are present in the addition polymer in an amount of less than 2% by weight, based on the total weight of the addition polymer. As used herein, an addition polymer is “essentially free” of structural units comprising the residue of isobutylene monomer if such structural units, if any, are present in the addition polymer in an amount of less than 0.1% by weight, based on the total weight of the addition polymer. As used herein, an addition polymer is “completely free” of structural units comprising the residue of isobutylene monomer if such structural units are not present in the addition polymer, i.e., 0.0% by weight.

[0039] The addition polymer may be substantially free, essentially free, or completely free of residues of monomers containing three or more ethylenically unsaturated groups per molecule. As used herein, an addition polymer is “substantially free” of residues of monomers containing three or more ethylenically unsaturated groups per molecule if such residues, if any, are present in the addition polymer in an amount of less than 0.1% by weight, based on the total weight of the addition polymer. As used herein, an addition polymer is “essentially free” of residues of monomers containing three or more ethylenically unsaturated groups per molecule if such residues, if any, are present in the addition polymer in an amount of less than 0.01% by weight, based on the total weight of the addition polymer. As used herein, an addition polymer is "completely free" of structural units comprising the residue of a monomer comprising three or more ethylenically unsaturated groups per molecule if such structural units are not present in the addition polymer, i.e., 0.00% by weight.

[0040] The addition polymer may be substantially free, essentially free, or completely free of silicon. As used herein, "silicon" refers to elemental silicon or any silicon-containing compound, such as organosilicon compounds including alkoxysilanes. As used herein, an addition polymer is "substantially free" of silicon if silicon is present in the addition polymer in an amount of less than 2% by weight, based on the total weight of the addition polymer. As used herein, an addition polymer is "essentially free" of silicon if silicon is present in the addition polymer in an amount of less than 1% by weight, based on the total weight of the addition polymer. As used herein, an addition polymer is "completely free" of silicon if silicon is not present in the addition polymer, i.e., 0% by weight.

[0041] The polymer comprising at least one phosphorylated group may include a phosphating epoxy resin. As used herein, the term "phosphating epoxy resin" refers to an ungelled resin derived from at least a polyepoxide and phosphoric acid, and explicitly excludes addition polymers such as (meth) acrylic polymers. The polyepoxide may include polyglycidyl ethers of polyphenols such as bisphenol A, such that the phosphating epoxy resin is an aromatic phosphating epoxy resin. Exemplary aromatic phosphating epoxy resins are provided in U.S. Patent Application Publication No. 2009 / 0045071

[0004] -

[0015] and U.S. Patent Application Serial No. 13 / 232,093

[0014] -

[0040] , the cited portions of which are incorporated herein by reference. Alternatively, the phosphating epoxy resin may be an aliphatic phosphating epoxy resin that is not an addition polymer. Polyesters, polyurethanes, polyethers, or polyamides prepared with glycidyl alcohol or glycidylamine or reacted with epihalohydrins are also suitable epoxy-functional resins. Epoxide functional groups can be incorporated into aliphatic resins by reacting the hydroxyl groups on the resin with an epihalohydrin or dihalohydrin (such as epichlorohydrin or dichloropropanol) in the presence of a base.The aliphatic epoxy resin can then be reacted with phosphoric acid.

[0042] The polymer comprising at least one phosphorylated group may have a hydroxyl value of at least 1, such as at least 10 mg KOH / g, such as at least 20 mg KOH / g, such as at least 50 mg KOH / g, such as at least 100 mg KOH / g, such as at least 200 mg KOH / g. The polymer may have a hydroxyl value of no more than 600 mg KOH / g, such as no more than 500 mg KOH / g, such as no more than 300 mg KOH / g, such as no more than 200 mg KOH / g. The polymer may have a mass fraction of 1 mg KOH / g to 600 mg KOH / g, such as 1 mg KOH / g to 500 mg KOH / g, such as 1 mg KOH / g to 300 mg KOH / g, such as 1 mg KOH / g to 200 mg KOH / g, such as 10 mg KOH / g to 600 mg KOH / g, such as 10 mg KOH / g to 500 mg KOH / g, such as 10 mg KOH / g to 300 mg KOH / g, such as 10 mg KOH / g to 200 mg KOH / g, such as 20 mg KOH / g to 600 mg KOH / g, such as 20 mg KOH / g to 500 mg KOH / g, such as 20 mg KOH / g to 300 mg KOH / g, such as 20 mg KOH / g to 200 mg KOH / g, such as 50 mg KOH / g to 600 mg KOH / g, such as 50 mg KOH / g to 500 mg KOH / g. KOH / g, such as 50 mg KOH / g to 300 mg KOH / g, such as 50 mg KOH / g to 200 mg KOH / g, such as 100 mg KOH / g to 600 mg KOH / g, such as 100 mg KOH / g to 500 mg KOH / g, such as 100 mg KOH / g to 300 mg KOH / g, such as 100 mg KOH / g to 200 mg KOH / g, such as 200 mg KOH / g to 600 mg KOH / g, such as 200 mg KOH / g to 500 mg KOH / g, such as 200 mg KOH / g to 300 mg KOH / g.

[0043] The polymer comprising at least one phosphorylated group may be present in the cationic electrodepositable coating composition in an amount of at least 0.01 wt %, such as at least 1 wt %, such as at least 5 wt %, such as at least 10 wt %, based on the total weight of the resin solids. The polymer comprising at least one phosphorylated group may be present in the cationic electrodepositable coating composition in an amount of no more than 50 wt %, such as no more than 30 wt %, such as no more than 20 wt %, such as no more than 15 wt %, based on the total weight of the resin solids. The polymer comprising at least one phosphated group can be present in the cationic electrodepositable coating composition in an amount of 0.01 wt % to 50 wt %, 0.01 wt % to 30 wt %, such as 0.01 wt % to 20 wt %, such as 0.01 wt % to 15 wt %, such as 1 wt % to 50 wt %, 1 wt % to 30 wt %, such as 1 wt % to 20 wt %, such as 1 wt % to 15 wt %, such as 5 wt % to 50 wt %, 5 wt % to 30 wt %, such as 5 wt % to 20 wt %, such as 5 wt % to 15 wt %, such as 10 wt % to 50 wt %, 10 wt % to 30 wt %, such as 10 wt % to 20 wt %, such as 10 wt % to 15 wt %, based on the total weight of the resin solids.

[0044] The cationically electrodepositable coating composition may comprise any suitable cationically electrodepositable binder. For example, the cationically electrodepositable binder may comprise an organic or inorganic electrodepositable binder.

[0045] As used herein, an "organic" electrodepositable adhesive comprises at least 50% by weight, such as at least 51% by weight, such as at least 75% by weight, such as at least 85% by weight, such as at least 95% by weight, such as at least 99% by weight, and may be 100% by weight of an organic-based material, based on the total weight of the electrodepositable adhesive. The organic film-forming adhesive may comprise from 51% to 100% by weight, such as from 75% to 100% by weight, such as from 85% to 100% by weight, such as from 95% to 100% by weight, such as from 99% to 100% by weight, such as from 100% by weight of an organic-based material, based on the total weight of the electrodepositable adhesive. The remainder of the adhesive may comprise an inorganic material present in an amount of less than 50% by weight, based on the total weight of the electrodepositable adhesive. The term "organic-based material" refers to a carbon-based material, such as the organic film-forming resin and organic curing agent described herein.

[0046] In contrast, as used herein, an "inorganic" electrodeposited adhesive comprises less than 50 wt%, such as less than 25 wt%, such as less than 15 wt%, such as less than 5 wt%, such as less than 1 wt%, and may be 0 wt% of organic-based materials, based on the total weight of the electrodeposited adhesive. An inorganic electrodeposited adhesive may comprise an inorganic-based material in an amount of 51 wt% to 100 wt%, such as 75 wt% to 100 wt%, such as 85 wt% to 100 wt%, such as 95 wt% to 100 wt%, such as 99 wt% to 100 wt%, such as 100 wt%, based on the total weight of the electrodeposited adhesive.

[0047] The cationic electrodepositable binder may be derived from a film-forming polymer containing a cationic salt group, and the cationic electrodepositable coating composition may include the film-forming polymer containing a cationic salt group. The film-forming polymer containing a cationic salt group may include a film-forming polymer containing a cationic salt group containing an active hydrogen.

[0048] In an example, the film-forming polymer containing a cationic salt group may include an aromatic film-forming polymer containing a cationic salt group. As used herein, "aromatic" refers to a hydrocarbon with a delocalized conjugated π-system in which double bonds and single bonds alternate between carbon atoms, thereby forming one or more coplanar hydrocarbon rings within the main chain of the polymer chain. For example, the aromatic film-forming polymer containing a cationic salt group may be at least partially derived from an aromatic compound, such as a diglycidyl ether of a bisphenol or a bisphenol (such as bisphenol A, bisphenol S and / or bisphenol F or its diglycidyl ether), a novolac resin, a diglycidyl ether or polyglycidyl ether of an alkylated phenol described below, and / or a diglycidyl ether of a dihydroxybenzene (such as catechol, resorcinol or hydroquinone). In contrast, an acrylic polymer containing a styrene residue, in which the aromatic group is present in the side chain of the acrylic polymer rather than as part of the main chain of the polymer chain, is not considered an "aromatic" film-forming polymer.

[0049] When present, the aromatic film-forming polymer containing cationic salt groups can be present in the cationic electrodepositable coating composition and the resulting electrodeposited coating in an amount of at least 10 wt %, such as at least 20 wt %, such as at least 30 wt %, such as at least 40 wt %, such as at least 50 wt %, such as at least 60 wt %, based on the total weight of the resin solids of the electrodepositable coating composition. The film-forming polymer containing cationic salt groups can be present in the cationic electrodepositable coating composition and the resulting electrodeposited coating in an amount of no more than 90 wt %, such as no more than 80 wt %, such as no more than 75 wt %, such as no more than 60 wt %, such as no more than 50 wt %, such as no more than 40 wt %, such as no more than 30 wt %, based on the total weight of the resin solids of the electrodepositable coating composition. The film-forming polymer containing cationic salt groups may be present in an amount of 10 wt % to 90 wt %, such as 10 wt % to 80 wt %, such as 10 wt % to 75 wt %, such as 10 wt % to 60 wt %, such as 10 wt % to 50 wt %, such as 20 wt % to 90 wt %, such as 20 wt % to 80 wt %, such as 20 wt % to 75 wt %, such as 20 wt % to 60 wt %, such as 20 wt % to 50 wt %, such as 30 wt % to 90 wt %, such as 30 wt % to 80 wt %, such as 30 wt % to 75 wt %, % by weight, such as 30 wt % to 60 wt %, such as 30 wt % to 50 wt %, such as 40 wt % to 90 wt %, such as 40 wt % to 80 wt %, such as 40 wt % to 75 wt %, such as 40 wt % to 60 wt %, such as 40 wt % to 50 wt %, such as 50 wt % to 90 wt %, such as 50 wt % to 80 wt %, such as 50 wt % to 75 wt %, such as 60 wt % to 90 wt %, such as 60 wt % to 80 wt %, such as 60 wt % to 75 wt %, present in the cationic electrodepositable coating composition and the resulting electrodepositable coating.

[0050] Film-forming polymers containing cationic salt groups can be used in coating compositions that can be electrodeposited by cations. As used herein, the term "film-forming polymers containing cationic salt groups" refers to polymers comprising cationic groups that are at least partially neutralized, such as sulfonium groups and ammonium groups that impart positive charge. As used herein, the term "polymer" encompasses but is not limited to oligomers and homopolymers and copolymers. Film-forming polymers containing cationic salt groups can include active hydrogen functional groups. The term "active hydrogen" refers to hydrogen, which, according to the Zerewitinoff test, shows activity due to the position of the hydrogen in the molecule, as described in JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, volume 49, page 3181 (1927). Therefore, active hydrogen includes a hydrogen atom connected to oxygen, nitrogen or sulfur, and therefore the active hydrogen functional group includes, for example, hydroxyl, thiol, carbamate, primary amino and / or secondary amino groups (in any combination). The cationic salt group-containing film-forming polymer comprising an active hydrogen functional group may be referred to as an active hydrogen-containing, cationic salt group-containing film-forming polymer.

[0051] Examples of polymers suitable for use as the film-forming polymer containing cationic salt groups in the present disclosure include, but are not limited to, alkyd polymers, acrylics, polyepoxides, polyamides, polyurethanes, polyureas, polyethers, polyesters, and the like.

[0052] More specific examples of suitable active hydrogen-containing, cationic salt group-containing film-forming polymers include polyepoxide-amine adducts, such as adducts of polyglycidyl ethers of polyphenols (such as bisphenol A) with primary and / or secondary amines, as described in U.S. Pat. No. 4,031,050 at column 3, line 27 to column 5, line 50, U.S. Pat. No. 4,452,963 at column 5, line 58 to column 6, line 66, and U.S. Pat. No. 6,017,432 at column 2, line 66 to column 6, line 26, portions of which are incorporated herein by reference. A portion of the amine reacted with the polyepoxide may be a ketimine of a polyamine, such as described in U.S. Pat. No. 4,104,147 at column 6, line 23 to column 7, line 23, the cited portions of which are incorporated herein by reference. Also suitable are ungelled polyepoxide-polyoxyalkylene polyamine resins such as those described in U.S. Pat. No. 4,432,850 at column 2, line 60 to column 5, line 58, the cited portions of which are incorporated herein by reference. Additionally, cationic acrylic resins such as those described in U.S. Pat. No. 3,455,806 at column 2, line 18 to column 3, line 61 and U.S. Pat. No. 3,928,157 at column 2, line 29 to column 3, line 21, both of which are incorporated herein by reference, may be used.

[0053] In addition to resins containing amine salt groups, resins containing quaternary ammonium salt groups can also be used as film-forming polymers containing cationic salt groups in the present disclosure. Examples of these resins are those formed by reacting organic polyepoxides with tertiary amine acid salts. Such resins are described in U.S. Patent No. 3,962,165, column 2, line 3 to column 11, line 7; No. 3,975,346, column 1, line 62 to column 17, line 25; and No. 4,001,156, column 1, line 37 to column 16, line 7, the portions of which are incorporated herein by reference. Examples of other suitable cationic resins include resins containing ternary sulfonium salt groups, such as those described in U.S. Patent No. 3,793,278, column 1, line 32 to column 5, line 20, the portions of which are incorporated herein by reference. Furthermore, it is also possible to employ cationic resins which cure via a transesterification mechanism, as described in European Patent Application No. 12463 B1, page 2, line 1 to page 6, line 25, this part of which is incorporated herein by reference.

[0054] Other suitable film-forming polymers containing cationic salt groups include those film-forming polymers that can form an electrodeposited coating composition that resists light degradation. Such polymers include polymers containing cationic amine salt groups, which are derived from side groups and / or terminal amino groups disclosed in U.S. Patent Application Publication No. 2003 / 0054193A1, paragraphs

[0064] to

[0088] , which are incorporated herein by reference. Equally suitable are resins containing active hydrogen and cationic salt groups derived from polyglycidyl ethers of polyphenols that are substantially free of aliphatic carbon atoms bonded to more than one aromatic group, which are disclosed in U.S. Patent Application Publication No. 2003 / 0054193A1, paragraphs

[0096] to

[0123] , which are incorporated herein by reference.

[0055] The film-forming polymer containing cationic salt groups may optionally include the reaction product of a reaction mixture comprising: (a) an aromatic polyepoxide; (b) a difunctional chain extender; and (c) a monofunctional reactant. Non-limiting examples of such polymers are provided in International Application No. PCT / US22 / 73356, paragraphs

[0023] to

[0038] , the cited portions of which are incorporated herein by reference.

[0056] Non-limiting examples of inorganic electrodepositable film-forming polymers include silicone-based film-forming polymers. Non-limiting examples of such polymers are described in paragraphs

[0007] to

[0029] of International Publication No. WO 2021 / 138384 Al, the cited portions of which are incorporated herein by reference.

[0057] By at least partial neutralization with an acid, the active hydrogen-containing, cationic salt group-containing film-forming polymer is cationic and water dispersible. Suitable acids include organic acids and inorganic acids. Non-limiting examples of suitable organic acids include formic acid, acetic acid, methanesulfonic acid, and lactic acid. Non-limiting examples of suitable inorganic acids include phosphoric acid and sulfamic acid. By “sulfamic acid” is meant sulfamic acid itself or a derivative thereof, such as sulfamic acid or a derivative thereof having the following formula:

[0058]

[0059] wherein R is hydrogen or an alkyl group having 1 to 4 carbon atoms. Mixtures of the above-mentioned acids can also be used in the present disclosure.

[0060] The degree of neutralization of the cationic salt group-containing film-forming polymer can vary depending on the particular polymer involved. However, sufficient acid should be used to adequately neutralize the cationic salt group-containing film-forming polymer so that the cationic salt group-containing film-forming polymer can be dispersed in an aqueous dispersion medium. For example, the amount of acid used can provide at least 20% of the total theoretical neutralization. An excess of acid beyond that required for 100% total theoretical neutralization can also be used. For example, the amount of acid used to neutralize the cationic salt group-containing film-forming polymer can be > 0.1% based on the total amine in the active hydrogen-containing, cationic salt group-containing film-forming polymer. Alternatively, the amount of acid used to neutralize the active hydrogen-containing, cationic salt group-containing film-forming polymer can be < 100% based on the total amine in the active hydrogen-containing, cationic salt group-containing film-forming polymer. The total amount of acid used to neutralize the cationic salt group-containing film-forming polymer can range between any combination of the values stated in the preceding sentences, inclusive of the stated values. For example, the total amount of acid used to neutralize the active hydrogen-containing, cationic salt group-containing film-forming polymer can be 20%, 35%, 50%, 60%, or 80% based on the total amine in the cationic salt group-containing film-forming polymer.

[0061] According to the present disclosure, the cationic salt group-containing film-forming polymer can be present in the cationic electrodepositable coating composition and the resulting electrodepositable coating in an amount of at least 40 weight %, such as at least 50 weight %, such as at least 60 weight %, based on the total weight of resin solids of the electrodepositable coating composition. The cationic salt group-containing film-forming polymer can be present in the cationic electrodepositable coating composition and the resulting electrodepositable coating in an amount of no more than 90 weight %, such as no more than 80 weight %, such as no more than 75 weight %, based on the total weight of resin solids of the electrodepositable coating composition. The cationic salt group-containing film-forming polymer can be present in the cationic electrodepositable coating composition and the resulting electrodepositable coating in an amount of 40 weight % to 90 weight %, such as 40 weight % to 80 weight %, such as 40 weight % to 75 weight %, such as 50 weight % to 90 weight %, such as 50 weight % to 80 weight %, such as 50 weight % to 75 weight %, such as 60 weight % to 90 weight %, such as 60 weight % to 80 weight %, such as 60 weight % to 75 weight %, based on the total weight of resin solids of the electrodepositable coating composition.

[0062] As used herein, "resin solids" include the cationic salt group-containing film-forming polymer, which polymer comprises at least one phosphated group, such as an addition polymer or a phosphated epoxy resin, a curing agent, and any additional water-dispersible non-pigmented components present in the electrodepositable coating composition.

[0063] The electrodepositable coating compositions of the present disclosure can further include a curing agent. The curing agent can react with the reactive groups, such as active hydrogen groups, of the cationic salt group-containing film-forming polymer, as well as any reactive groups, if present, of any additional resinous material, to effect curing of the electrodepositable coating composition to form a coating. Non-limiting examples of suitable curing agents include at least partially blocked polyisocyanates, as well as aminoplast resins and / or phenoplast resins, such as phenol formaldehyde condensates, including allyl ether derivatives thereof.

[0064] As used herein, the term "curing", "cured" or similar terms used in conjunction with the electrodepositable coating compositions described herein means that at least a portion of the components of the electrodepositable coating composition are cross-linked to form a cross-linked coating. Additionally, curing of the electrodepositable coating composition refers to subjecting the electrodeposited composition to curing conditions (e.g., elevated temperature) that result in a reaction of the reactive functional groups of the components of the electrodepositable coating composition, and results in cross-linking of the components of the composition and the formation of an at least partially cured coating. As used herein, the term "at least partially cured" with respect to a coating refers to forming a coating by subjecting the coating composition to curing conditions that chemically react at least a portion of the reactive groups of the components of the coating composition to form a coating. The coating composition may also be subjected to curing conditions such that a substantially complete cure is achieved, and wherein further curing does not further significantly improve the coating properties, such as, for example, solvent resistance or hardness.

[0065] As used herein, "blocked polyisocyanate" means a polyisocyanate in which at least a portion of the isocyanate groups are blocked by blocking groups introduced by reaction of free isocyanate groups of the polyisocyanate with a blocking agent. "Blocked" means that the isocyanate groups have reacted with the blocking agent such that the resulting blocked isocyanate groups are stable to active hydrogen at ambient temperature, for example, room temperature (23°C). This reaction can be reversed under suitable conditions, such as at an elevated temperature, such as, for example, between 90°C and 200°C, such that the previously blocked isocyanate groups on the polyisocyanate curing agent are unblocked and available to react with reactive groups (such as active hydrogen groups) of the film-forming polymer containing cationic salt groups to effect curing of the coating composition to form a coating.

[0066] As used herein, "blocking agent" refers to a compound containing a functional group that can react with an isocyanate group to form a blocked isocyanate. As used herein, "blocking group" refers to the remaining portion of the blocking agent that is bound to the isocyanate group in the blocked polyisocyanate.

[0067] The blocking agent separated from the blocked polyisocyanate curing agent during curing can be removed from the coating film by volatilization. Alternatively, a portion or all of the blocking agent can remain in the coating film after curing.

[0068] Non-limiting examples of blocked polyisocyanate curing agents including suitable polyisocyanates and blocking components (such as blocking groups) and / or blocking agents (such as, but not limited to, 1,2 polyols), and amounts thereof, are provided in International Publication No. WO2021 / 138583A1, paragraphs

[0022] to

[0035] , the cited portions of which are incorporated herein by reference.

[0069] Non-limiting examples of blocked polyisocyanates comprising blocking groups derived from blocking agents (including α-hydroxyamides, esters, or thioesters) and optional second blocking agents are provided in International Publication No. WO 2018 / 148306 A1, 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 isocyanate 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 in which less than 100% of the isocyanate groups are blocked, as long as the coating composition maintains a stable dispersion as defined herein.

[0070] The at least partially blocked polyisocyanate may be partially blocked with one or more blocking groups as discussed above, with the remaining isocyanate groups reacting with the polymer backbone, such as described in U.S. Pat. No. 3,947,338 at column 2, line 65 to column 5, line 33, the cited portions of which are incorporated herein by reference.

[0071] The blocked polyisocyanate curing agent may comprise tris(alkoxycarbonylamino)-1,3,5-triazine (TACT). Non-limiting examples of suitable tris(alkoxycarbonylamino)-1,3,5-triazines include tris(methoxycarbonylamino)-, tris(butoxycarbonylamino)-, and tris(2-ethylhexyloxycarbonylamino)-1,3,5-triazines, and any combination thereof.

[0072] The curing agent may include an aminoplast or phenoplast resin. An aminoplast resin is a condensation product of an aldehyde with a substance carrying an amino or amide group. A phenoplast resin is formed by the condensation of an aldehyde and a phenol.

[0073] Non-limiting examples of commercially available aminoplast resins are those sold under the trademark HYDROGEN(R) from Allnex Belgium SA / NV. (such as CYMEL 1130 and 1156) and products from INEOS Melamines under the trademark Aminoplast resins such as those commercially available from RESIMENE 750 and 753. Examples of suitable aminoplast resins and amounts thereof also include those described in U.S. Patent No. 3,937,679 at column 16, line 3 to column 17, line 47, this portion of which is hereby incorporated by reference. As disclosed in the preceding portion of the '679 patent, aminoplasts can be used in combination with methanol phenol ethers.

[0074] Suitable aminoplast resins and phenoplast resins are also further described in US Patent No. 4,812,215 at column 6, line 20 to column 7, line 12, the cited portions of which are incorporated herein by reference.

[0075] Non-limiting examples of inorganic curing agents include silicone-based curing agents. Non-limiting examples of such curing agents are described in International Publication No. WO 2021 / 138384 A1, paragraphs

[0030] to

[0043] , the cited portions of which are incorporated herein by reference.

[0076] The curing agent may be present in the electrodepositable coating composition in an amount of at least 10 wt %, such as at least 20 wt %, such as at least 25 wt %, 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 wt %, such as no more than 50 wt %, such as no more than 45 wt %, such as no more than 40 wt %, 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 wt %, such as 10 to 50 wt %, such as 10 to 45 wt %, such as 10 to 40 wt %, such as 20 to 60 wt %, such as 20 to 50 wt %, such as 20 to 45 wt %, such as 20 to 40 wt %, such as 25 to 60 wt %, such as 25 to 50 wt %, such as 25 to 45 wt %, such as 25 to 40 wt %, based on the total weight of the resin solids of the electrodepositable coating composition.

[0077] The electrodepositable coating composition may further comprise a curing catalyst. As used herein, the term "curing catalyst" is used interchangeably with "catalyst" and refers to a material that catalyzes the curing reaction between the components of the electrodepositable coating composition, such as, for example, the curing agent and the film-forming polymer. For example, the catalyst may catalyze the transcarbamation reaction, and in particular, catalyze the deblocking of blocked polyisocyanate end groups.

[0078] Non-limiting examples of curing catalysts include amine-containing compounds; compounds or complexes of metals such as bismuth, cerium, zinc, and / or titanium; and combinations thereof.

[0079] Catalysts suitable for use in the cationic electrodepositable coating compositions include, but are not limited to, metal oxides (e.g., oxides of cerium, zirconium, and bismuth) and salts thereof; zinc compounds or complexes; and / or cyclic guanidines as described in U.S. Patent No. 7,842,762 at column 1, line 53 to column 4, line 18 and column 16, line 62 to column 19, line 8, the cited portions of which are incorporated herein by reference.

[0080] Catalysts suitable for use in anionic electrodepositable coating compositions include, but are not limited to, latent acid catalysts. Latent acid catalysts are derivatives of acid catalysts typically activated by heating. Non-limiting examples of latent acid catalysts are described in WO 2007 / 118024, paragraph

[0031] . Other examples of suitable latent acid catalysts include derivatives of acid catalysts, such as sulfonic acids, such as derivatives of p-toluenesulfonic acid, such as pyridinium p-toluenesulfonate.

[0081] The amine-containing curing catalyst may include any suitable amine-containing curing catalyst, such as, but not limited to, a curing catalyst comprising guanidine, imidazole, amidine, and / or derivatives or combinations thereof.

[0082] Non-limiting examples of suitable guanidine curing catalysts are provided in International Publication No. WO 2018 / 0172519 A1, paragraphs

[0039] to

[0050] , the cited portions of which are incorporated herein by reference.

[0083] Non-limiting examples of imidazole curing catalysts are described in U.S. Publication No. 2022 / 0154014 Al, paragraphs

[0062] to

[0108] , the cited portions of which are incorporated herein by reference.

[0084] In a non-limiting example, the amidine cure catalyst can include 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0085] The zinc-containing catalyst may include a metal salt and / or complex of zinc, such as, but not limited to, zinc (II) amidine complex, zinc octoate, zinc naphthenate, zinc tall oil acid, zinc carboxylates (the number of carbon atoms in the carboxylate group is 8 to 14), zinc acetate, zinc sulfonate, zinc methanesulfonate, or any combination thereof. The zinc (II) amidine complex may contain an amidine and a carboxylic acid ligand.

[0086] The curing catalyst may be present in the electrodepositable coating composition in any suitable amount. For example, based on the total weight of the resin solids in the coating composition, the amine-containing and / or zinc curing catalyst may be present in the coating composition in an amount of at least 0.1 wt %, such as at least 0.2 wt %, such as at least 0.5 wt %, such as at least 0.8 wt %, such as at least 1 wt %, such as at least 1.5 wt %. Based on the total weight of the resin solids in the coating composition, the amine-containing and / or zinc curing catalyst may be present in the coating composition in an amount of no more than 7 wt %, such as no more than 4 wt %, such as no more than 2 wt %, such as no more than 1.5 wt %, such as no more than 1 wt %. Based on the total weight of the resin solids of the coating composition, the amine and / or zinc curing catalyst may be present in an amount of 0.1 wt % to 7 wt %, such as 0.1 wt % to 4 wt %, such as 0.1 wt % to 2 wt %, such as 0.1 wt % to 1.5 wt %, such as 0.1 wt % to 1 wt %, such as 0.2 wt % to 7 wt %, such as 0.2 wt % to 4 wt %, such as 0.2 wt % to 2 wt %, such as 0.2 wt % to 1.5 wt %, such as 0.2 wt % to 1 wt %, such as 0.5 wt % to 7 wt %, such as 0.5 wt % to 4 wt %, such as 0.5 wt % to % to 7 wt %, such as 0.8 wt % to 4 wt %, such as 0.8 wt % to 2 wt %, such as 0.8 wt % to 1.5 wt %, such as 0.8 wt % to 1 wt %, such as 1 wt % to 7 wt %, such as 1 wt % to 4 wt %, such as 1 wt % to 2 wt %, such as 1 wt % to 1.5 wt %, such as 1.5 wt % to 7 wt %, such as 1.5 wt % to 4 wt %, such as 1.5 wt % to 2 wt %, such as 1 wt % to 1.5 wt %, such as 1.5 wt % to 7 wt %, such as 1.5 wt % to 4 wt %, such as 1.5 wt % to 2 wt %.

[0087] The curing catalyst may include a bismuth catalyst. Non-limiting examples of bismuth curing catalysts and amounts thereof are provided in International Publication No. WO 2021 / 138583 A1, paragraphs

[0036] to

[0050] , the cited portions of which are incorporated herein by reference.

[0088] The curing catalyst may comprise a titanium compound and / or complex, such as, for example, Ti(OR 1 )4, where R 1 is an alkyl or aryl group, such as where R 1 is a C3-C20 alkyl group, such as wherein R 1 is n-butyl, such as tetrabutyl titanate.

[0089] The electrodepositable coating composition may be substantially free, substantially free, or completely free of catalytic tin. The electrodepositable coating composition may be substantially free, substantially free, or completely free of catalytic tin. As used herein, an electrodepositable coating composition is "substantially free" of catalytic tin if the catalytic tin is present in an amount of less than 0.1 weight percent, based on the total weight of the electrodepositable coating composition. As used herein, an electrodepositable coating composition is "substantially free" of catalytic tin if the catalytic tin is present in an amount of less than 0.01 percent, based on the total weight of the electrodepositable coating composition. As used herein, an electrodepositable coating composition is "completely free" of catalytic tin if the catalytic tin is present in an amount of 0.001 percent, based on the total weight of the electrodepositable coating composition.

[0090] The electrodepositable coating composition may further comprise a pigment. Non-limiting examples of pigments include, for example, iron oxide, lead oxide, strontium chromate, carbon black, coal dust, titanium dioxide, talc, barium sulfate, thermally conductive electrically insulating filler materials, thermally conductive electrically conductive filler materials, non-thermally conductive electrically insulating filler materials, flame retardant pigments, and color pigments such as cadmium yellow, cadmium red, chrome yellow, and the like.

[0091] The pigment may include a platy pigment, such as an inorganic platy pigment.

[0092] The plate-like pigment may be a phyllosilicate pigment. As used herein, the term "phyllosilicate" refers to a group of minerals having silicate sheets, the basic structure of which is based on interconnected SiO4 -4 The six-membered ring of the tetrahedron extends outward in an infinite layer, wherein three of the four oxygens of each tetrahedron are shared with other tetrahedrons, thereby producing the basic structural unit Si2O5 -2 The layered silicate may contain hydroxide ions and / or cations such as Fe +2 Mg +2 or Al +3 , these ions form cationic layers between the silicate sheets, wherein the cations can coordinate with the oxygen and / or hydroxide ions of the silicate layers. The term "phyllosilicate pigment" refers to a pigment material comprising phyllosilicates. Non-limiting examples of phyllosilicate pigments include mica, chlorite, serpentine, talc and clay minerals. Clay minerals include, for example, kaolin clay. The sheet-like structure of phyllosilicate pigments tends to give the pigment a plate-like structure, but the pigment can be manipulated (such as by mechanical means) to have other particle structures. These pigments may or may not swell when exposed to a liquid medium and may or may not have leachable components (e.g., ions that can be attracted toward the liquid medium).

[0093] The platy pigments can include platy mica pigments, platy chlorite pigments, platy serpentine pigments, platy talc pigments, and / or platy clay pigments. The platy clay pigments can include kaolin clay or combinations thereof.

[0094] The pigment component can include platy pigments having an average equivalent spherical diameter of at least 50 nm and up to 25 microns or more. The average equivalent spherical diameter can be determined using dynamic light scattering, such as with a SEDIGRAPH III PLUS particle size analyzer available from Micromeritics Instrument Corp. As platy particles, the pigments generally have substantially opposed surfaces, and the particles generally exhibit an aspect ratio of the longest axis to the shortest axis that is generally 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 more. For example, the platy pigments can 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 platy pigments can 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 micron.

[0095] As used herein, “flame retardant” refers to a material that slows or stops the spread of fire or reduces its intensity. Flame retardants can be obtained as a powder that can be mixed with a composition, foam, or gel. In examples, when a cationically electrodepositable coating composition includes a flame retardant, such compositions can form a coating on a substrate surface, and such coatings can function as a flame retardant coating.

[0096] As set out in greater detail below, the flame retardant can include a mineral, an organic compound, an organic halogen compound, an organic phosphorus compound, or combinations thereof.

[0097] Suitable examples of minerals include huntite, hydro magnesite, various hydrates, red phosphorus, boron compounds such as borates, carbonates such as calcium carbonate and magnesium carbonate, and combinations thereof.

[0098] Suitable examples of organohalogen compounds include organochlorines such as chlorobridgeic acid derivatives and chlorinated paraffins; organobromines such as decabromodiphenyl ether (decaBDE), decabromodiphenyl ethane (a substitute for decaBDE), polymeric brominated compounds such as brominated polystyrene, brominated carbonate oligomers (BCO), brominated epoxy resin oligomers (BEO), tetrabromophthalic anhydride, tetrabromobisphenol A (TBBPA), and hexabromocyclododecane (HBCD). Such halogenated flame retardants can be used in conjunction with synergists to enhance their effectiveness. Other suitable examples include antimony trioxide, antimony pentoxide, and sodium antimonate.

[0099] Suitable examples of organophosphorus compounds include triphenyl phosphate (TPP), resorcinol bis(diphenyl phosphate) (RDP), bisphenol A diphenyl phosphate (BADP), and tricresyl phosphate (TCP); phosphonates such as dimethyl methylphosphonate (DMMP); and phosphites such as aluminum diethylphosphite. In an important class of flame retardants, compounds contain both phosphorus and halogens. Such compounds include tris(2,3-dibromopropyl) phosphate (tribromide) and chlorinated organophosphates such as tris(1,3-dichloro-2-propyl) phosphate (trichloro or TDCPP) and tetrakis(2-chloroethyl)dichloroisopentyl diphosphate (V6).

[0100] Suitable examples of organic compounds include carboxylic acids, dicarboxylic acids, melamine and organic nitrogen compounds.

[0101] Other suitable flame retardants include ammonium polyphosphate and barium sulfate.

[0102] The pigment to binder (P:B) ratio described in the present disclosure can refer to the weight ratio of pigment to binder in the electrodepositable coating composition, and / or the weight ratio of pigment to binder in the deposited wet film, and / or the weight ratio of pigment to binder in the dried uncured deposited film, and / or the weight ratio of pigment to binder in the cured film.

[0103] The pigment to the electrodepositable binder (P:B) ratio 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 0.30:1, 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 the electrodepositable binder (P:B) ratio may be no more than 2:1, such as no more than 1.75:1, such as 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 to 0.55:1, 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.

[0104] The pigment to binder (P:B) ratio of the inorganic plate-shaped 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 0.7:1, 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 inorganic plate-shaped pigment to the electrodepositable binder may be no more than 2:1, such as no more than 1.75:1, such as 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-shaped 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 0.7:1 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 1.7 5:1, 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.

[0105] The electrodepositable coating composition may optionally contain a dispersant to assist in dispersing the pigment and other optional filler materials.

[0106] The electrodepositable composition may optionally include a corrosion inhibitor. Any suitable corrosion inhibitor may be used. For example, the corrosion inhibitor may include one comprising yttrium, lanthanum, cerium, calcium, azole, or any combination thereof.

[0107] Non-limiting examples of suitable azoles include benzotriazole, 5-methylbenzotriazole, 2-aminothiazole, and salts thereof.

[0108] The corrosion inhibitor, if any, may be present in the electrodepositable coating composition in an amount of at least 0.001 wt %, such as at least 5 wt %, based on the total weight of the electrodepositable coating composition. The corrosion inhibitor may be present in the electrodepositable coating composition in an amount of no more than 25 wt %, such as no more than 15 wt %, such as no more than 10 wt %, based on the total weight of the electrodepositable coating composition.

[0109] Alternatively, the electrodepositable coating composition may be substantially free, essentially free, or completely free of corrosion inhibitors.

[0110] According to the present disclosure, the electrodepositable coating composition may contain other optional ingredients, such as, if desired, various additives such as fillers, plasticizers, antioxidants, biocides, UV light absorbers and stabilizers, hindered amine light stabilizers, defoamers, fungicides, dispersing aids, flow control agents, surfactants, wetting agents, or combinations thereof. Each of the optional additional ingredients mentioned above may be present in the electrodepositable coating composition in an amount of 0.01 wt % to 3 wt %, based on the total weight of the resin solids of the electrodepositable coating composition. Alternatively, the electrodepositable coating composition may be completely free of any optional ingredients, i.e., the optional ingredients are not present in the electrodepositable coating composition.

[0111] According to the present disclosure, the coating composition that can be electrodeposited can include water and / or one or more organic solvents. Based on the gross weight of the coating composition that can be electrodeposited, water can, for example, exist in an amount of 40 wt % to 90 wt % (such as 50 wt % to 75 wt %). The example of a suitable organic solvent includes an oxygen-containing organic solvent, such as the monoalkyl ether containing 1 to 10 carbon atoms in the alkyl group of ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol, such as the monoethyl ether and monobutyl ether of these glycols. Other examples of water-miscible solvents at least in part include alcohols, such as ethanol, isopropanol, butanol and diacetone alcohol. If used, then based on the gross weight of the coating composition that can be electrodeposited, the organic solvent can generally exist in an amount less than 10 wt % (such as less than 5 wt %). The coating composition that can be electrodeposited can specifically be provided in the form of a dispersion (such as an aqueous dispersion).

[0112] 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 20% by weight, based on the total weight of the electrodepositable coating composition. The total solids content of the electrodepositable coating composition may be from 1% to 50% by weight, such as from 5% to 40% by weight, such as from 5% to 20% 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 that will not volatilize when heated to 110° C. for 15 minutes.

[0113] According to the present disclosure, a coating formed from the electrodepositable coating composition as deposited can be electrophoretically applied to a conductive substrate. The electrodepositable coating composition can be electrophoretically deposited on any conductive substrate. Suitable substrates include metal substrates, metal alloy substrates, and / or metallized substrates, such as nickel-plated plastic. Additionally, the substrate can comprise non-metallic, electrically conductive materials, including composites, such as, for example, materials comprising carbon fibers or electrically conductive carbon. According to the present disclosure, the metal or metal alloy can include cold rolled steel, hot rolled steel, steel coated with zinc metal, zinc compounds, or zinc alloys, such as electrogalvanized steel, hot-dipped galvanized steel, galvannealed steel, and steel plated with zinc alloys. Aluminum alloys of the 2XXX, 3XXX, 4XXX, 5XXX, 6XXX, or 7XXX series, as well as composite aluminum alloys and cast aluminum alloys of the A356 series can also be used as substrates. Magnesium alloys of the AZ31B, AZ91C, AM60B, or EV31A series can also be used as substrates. The substrates used in the present disclosure can also include titanium and / or titanium alloys. Other suitable non-ferrous metals include copper and magnesium, and alloys of these materials. Suitable metal substrates for use in the present disclosure include metal substrates typically used in assemblies of vehicle bodies (such as, but not limited to, doors, body panels, trunk lids, roof panels, hoods, roof and / or stringers, rivets, landing gear assemblies, and / or skins used on aircraft), vehicle frames, vehicle parts, motorcycles, vehicle wheels, industrial structures and assemblies, such as household appliances including washing machines, dryers, refrigerators, stoves, dishwashers, and the like, agricultural equipment, lawn and garden equipment, air conditioning units, heat pump units, lawn furniture, and other articles. As used herein, “vehicle” or variations thereof includes, but is not limited to, civilian, commercial, and military aircraft and / or land vehicles, such as automobiles, motorcycles, and / or trucks. The metal substrate can also be in the form of, for example, a metal sheet or a preformed part. It will also be appreciated that the substrate can be pretreated with a pretreatment solution including a zinc phosphate pretreatment solution, such as, for example, those described in U.S. Patent Nos. 4,793,867 and 5,588,989, or a zirconium-containing pretreatment solution, such as, for example, those described in U.S. Patent Nos. 7,749,368 and 8,673,091, all U.S. Patents incorporated herein by reference.

[0114] In examples, the substrate can be a multi-metallic article. As used herein, the term “multi-metallic article” means (1) an article having at least one surface comprising a first metal and at least one surface comprising a second metal different from the first metal, (2) a first article having at least one surface comprising a first metal and a second article having at least one surface comprising a second metal different from the first metal, or (3) both (1) and (2).

[0115] In an example, the substrate may include a battery or battery assembly. The battery assembly may include, but is not limited to, a battery cell, a battery housing, a battery module, a battery pack, a battery box, a battery cell housing, a battery pack housing, a battery cover and tray, a thermal management system, a battery housing, a module housing, a module bracket, a battery side panel, a battery cell housing, a cooling module, a cooling tube, a cooling fin, a cooling plate, a bus bar, a battery frame, an electrical connector, a metal wire or a copper or aluminum conductor or cable. The battery may be, for example, an electric vehicle battery, and the battery assembly may be, for example, an electric vehicle battery assembly.

[0116] In an example, the substrate may include a three-dimensional component formed by an additive manufacturing process such as selective laser melting, electron beam melting, directed energy deposition, binder jetting, metal extrusion, etc. In an example, the three-dimensional component may be a metal and / or resin component, as long as the three-dimensional component is conductive.

[0117] According to the present disclosure, the coating composition of the cation electrodeposition of the present disclosure can be deposited on a conductive substrate by contacting the composition with a conductive cathode and a conductive anode, wherein the surface to be coated is a cathode. After contacting with the composition, when applying enough voltages between the electrodes, the adhesive film of the coating composition is deposited on the cathode. The condition for carrying out electrodeposition is similar to the conditions employed in the electrodeposition of other types of coatings usually. The voltage applied can change and can be, for example, as low as one volt to as high as several thousand volts, such as between 50 volts and 500 volts. The current density can be between 0.5 ampere and 15 amperes per square foot, and tends to reduce during the electrodeposition, which shows that an insulating film has been formed.

[0118] Once the cationic electrodepositable coating composition is electrodeposited on at least a portion of a conductive substrate, the coated substrate is heated to a temperature and for a time sufficient to at least partially cure the electrodeposited coating on the substrate. As used herein, the term "at least partially cured" with respect to a coating refers to forming a coating by subjecting the coating composition to curing conditions that chemically react at least a portion of the reactive groups of the components of the coating composition to form a coating. The coated substrate can be heated to a temperature ranging from 250°F to 450°F (121.1°C to 232.2°C), such as 275°F to 400°F (135°C to 204.4°C), such as 300°F to 360°F (149°C to 180°C). Curing time can depend on curing temperature and other variables, for example, the film thickness of the electrodeposited coating, the level and type of the catalyst present in the composition, etc. For the purposes of this disclosure, all that is necessary is that time is sufficient to achieve the curing of the coating on the substrate. For example, the curing time may range from 10 minutes to 60 minutes, such as from 20 minutes to 40 minutes.The thickness of the resulting cured electrodeposited coating may range from 15 to 50 microns.

[0119] The present disclosure also relates to a method for coating a metal substrate, comprising: (1) immersing a surface of the metal substrate to be coated in a cationic electrodepositable coating composition, the cationic electrodepositable coating composition comprising: (a) a film-forming polymer containing cationic salt groups; (b) a curing agent; and (c) a phosphate ion source or a polymer containing at least one phosphated group, wherein the metal substrate serves as a cathode electrically connected to an anode immersed in the cationic electrodepositable coating composition; (2) allowing the immersed metal substrate to remain in the cationic electrodepositable coating composition for a certain period of time, thereby forming a metal phosphate layer on at least a portion of the surface of the metal substrate; and (3) applying a direct current between the cathode and the anode, thereby depositing a coating formed from the cationic electrodepositable coating composition on the surface of the metal substrate.

[0120] The residence time can be at least 10 seconds, such as at least 30 seconds, such as at least 1 minute, such as at least 4 minutes, such as at least 5 minutes, such as at least 8 minutes, such as at least 10 minutes, such as at least 12 minutes, such as at least 15 minutes or longer.The residence time also can be less than 15 minutes, less than 12 minutes, less than 10 minutes, less than 8 minutes, less than 5 minutes, less than 4 minutes, less than 1 minute or less than 30 seconds.The residence time can be 10 seconds to 15 minutes, such as 10 seconds to 12 minutes, such as 10 seconds to 10 minutes, such as 10 seconds to 8 minutes, such as 10 seconds to 5 minutes, such as 10 seconds to 4 minutes, such as 10 seconds to 1 minute, such as 10 seconds to 30 seconds.As mentioned above, the residence of substrate causes the generation of metal phosphate layer on at least a portion of the surface of metal substrate, makes that the residence in the coating composition that can be electrodeposited serves as pseudo pretreatment composition application.As used herein, " pretreatment composition " refers to and can react with substrate surface and chemically change substrate surface and be combined with it to form the composition of film / layer.

[0121] Optionally, the metal substrate is not treated with a pretreatment composition (such as a zinc phosphate or zirconium-containing pretreatment composition) prior to immersion in the cationic electrodepositable coating composition.

[0122] After the substrate remains in the cationic electrodepositable coating composition for a certain period of time, a direct current is applied between the electrodes to deposit a coating formed from the cationic electrodepositable coating composition on the surface of the metal substrate by a typical procedure in the art, such as the conditions described above (e.g., voltage, current density, time, etc.).

[0123] The present disclosure also relates to a method of coating a metal substrate comprising: (1) submerging a surface of a metal substrate to be coated into a cationic electrodepositable coating composition comprising: (a) a film-forming polymer comprising cationic salt groups; (b) a curing agent; and (c) a source of phosphate ions or a polymer comprising at least one phosphated group, wherein the metal substrate is used as an electrode in electrical communication with a counter electrode submerged in the cationic electrodepositable coating composition; (2) applying a direct current between the electrode and the counter electrode, wherein the electrode is used as an anode and the counter electrode is used as a cathode, thereby forming a metal phosphate layer over at least a portion of the surface of the metal substrate; and (3) applying a direct current between the electrode and the counter electrode, wherein the polarity is reversed and the electrode is used as a cathode and the counter electrode is used as an anode, thereby depositing a coating formed from the cationic electrodepositable coating composition on the surface of the metal substrate.

[0124] The direct current applied in part (2) of the method is the reverse polarity of the direct current applied in depositing the coating formed from the electrodepositable coating composition. The voltage applied can vary and can be as low as 1.5 volts to as high as 20 volts, such as between 5 volts and 15 volts, the current density can be between 0.5 amps and 15 amps per square foot, and the time for which the current is applied can vary and can be, for example, at least 1 minute, such as at least 2 minutes, such as at least 4 minutes or more.

[0125] Optionally, the metal substrate is not treated with a pretreatment composition, such as a zinc phosphate or zirconium-containing pretreatment composition, prior to submerging in the cationic electrodepositable coating composition.

[0126] After applying the reverse polarity direct current, a direct current is applied between the electrodes to deposit the coating formed from the cationic electrodepositable coating composition onto the surface of the metal substrate by procedures typical in the art, such as the conditions described above (e.g., voltage, current density, time, etc.).

[0127] Without intending to be bound by theory, it is believed that submerging or applying a reverse polarity current to the substrate prior to electrodeposition of the coating formed from the electrodepositable coating composition allows the phosphate ions or the polymer comprising at least one phosphated group to interact with the surface of the metal substrate to produce a metal phosphate layer over at least a portion of the surface of the substrate. This can allow elimination of a pretreatment step prior to electrodeposition of the substrate, such as elimination of treating the substrate with a zinc phosphate, iron phosphate, or zirconium-containing pretreatment composition.

[0128] The present disclosure also relates to a method for coating a metal substrate, comprising: (1) immersing a surface of the metal substrate to be coated into a cationic electrodepositable coating composition, the cationic electrodepositable coating composition comprising: (a) a film-forming polymer containing cationic salt groups; (b) a curing agent; and (c) a phosphate ion source or a polymer containing at least one phosphated group, wherein the metal substrate serves as an electrode electrically connected to a counter electrode immersed in the cationic electrodepositable coating composition; and (2) applying a direct current between the electrode and the counter electrode, thereby depositing a coating formed from the cationic electrodepositable coating composition on the surface of the metal substrate; wherein the metal substrate has not been treated with a pretreatment composition prior to immersion in the cationic electrodepositable coating composition.

[0129] The metal substrate to be coated may first be cleaned to remove grease, dirt, or other foreign matter. Conventional cleaning procedures and materials may be used. These materials may include, for example, mild or strongly alkaline detergents, such as those commercially available. Application of such detergents may be preceded or followed by a water rinse.

[0130] After cleaning with the alkaline cleaner, the metal surface may then optionally be rinsed with an aqueous acid solution. Examples of suitable rinse solutions include mild or strong acidic cleaners, such as commercially available dilute nitric acid solutions.

[0131] After applying the coating that is formed by the coating composition of the electrodeposited coating of cation, the method can also optionally comprise applying additional coating composition, to form one or more suitable topcoats on the coating of electrodeposition (for example, basecoat, clearcoat, colored single coating and colored+transparent composite composition).Should be appreciated that suitable topcoat layer comprises any coating in those coatings as known in the art, and can be independently of one another water-based, solvent-based, in solid particulate form (that is, powder coating composition) or in the form of powder slurry.Topcoat comprises film-forming polymer, crosslinking material and one or more pigments (if being colored basecoat or single coating).According to the disclosure, one or more topcoat layers can be applied to basically uncured bottom layer.For example, clearcoat can be applied to basically uncured basecoat (wet-on-wet) at least a portion, and can solidify two layers simultaneously in downstream process.

[0132] As noted above, additional ingredients such as colorants and fillers may be present in the various coating compositions that produce the topcoat layer. Any suitable colorant and filler can be used. For example, colorant can be added to the coating in any suitable form such as discrete particles, dispersions, solutions and / or flakes. Single colorant or a mixture of two or more colorants can be used in the coating of the present disclosure. It should be noted that generally, colorant can be present in the layer of the multilayer coating composite material in any amount that is enough to impart desired properties, visual and / or color effects.

[0133] The present disclosure further relates to coatings formed by at least partially curing a deposited film formed from the electrodepositable coating compositions described herein.

[0134] The present disclosure further relates to coated substrates coated with a deposited coating formed from a cationic electrodepositable coating composition as described herein. Additionally, the coated substrates optionally can be coated by any of the methods described herein.

[0135] The coated substrate optionally may not include a pretreatment layer between the substrate and the deposited coating formed from the cationic electrodepositable coating composition.

[0136] The coated conductive substrate optionally may not include any intervening coatings between the substrate and the deposited coating formed from the cationic electrodepositable coating composition.

[0137] For the purposes of this detailed description, it should be understood that the present disclosure may take alternative variations and step sequences, except where expressly stated otherwise. Furthermore, except in any operating examples or where otherwise indicated, all numerals representing, for example, the amounts of ingredients used in the specification and claims should be understood to be modified in all cases by the term "about". Therefore, unless otherwise indicated, the numerical parameters set forth in the following specification and the appended claims are approximate values ​​that may vary depending on the desired properties to be obtained by the present disclosure. At a minimum, and not attempting to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be interpreted in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0138] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values ​​set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0139] Furthermore, it should be understood that any numerical range recited herein is intended to include all subranges subsumed therein. For example, a range of "1 to 10" is intended to include all subranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, i.e., having a minimum value equal to or greater than 1 and a maximum value equal to or less than 10.

[0140] As used herein, "comprising," "containing," and similar terms are understood in the context of this application to be synonymous with "comprising" and are therefore open-ended and do not exclude the presence of additional undescribed or unnarrated elements, materials, ingredients, or method steps. However, they also include the more restrictive terms "consisting of" and "consisting essentially of." As used herein, "consisting of" is understood in the context of this application to exclude the presence of any unspecified elements, ingredients, or method steps. As used herein, "consisting essentially of" is understood in the context of this application to include the specified elements, materials, ingredients, or method steps "as well as those elements, materials, ingredients, or method steps that do not materially affect the basic and novel characteristics of what is described."

[0141] In this application, unless otherwise expressly stated, the use of the singular includes the plural and the plural encompasses the singular. For example, although this document mentions "a" cationic salt group-containing aromatic film-forming polymer, "a" cationic salt group-containing film-forming polymer, "a" addition polymer, "a" polymer containing at least a phosphate group, "a" monomer, "a" curing agent, "a" pigment, "a" inorganic plate-like pigment, combinations of these components (i.e., multiple components) may also be used. In addition, in this application, unless otherwise expressly stated, the use of "or" means "and / or", even if "and / or" can be clearly used in certain cases.

[0142] While specific aspects of the present disclosure have been described in detail, those skilled in the art will appreciate that various modifications and alternatives to those details can be developed based on the overall teachings of the present disclosure. Therefore, the particular arrangements disclosed are intended to be illustrative only and not limiting of the scope of the present disclosure, which is to be given by the full scope of the appended claims and any and all equivalents thereof.

[0143] The following examples illustrate the present disclosure, which, however, should not be considered to limit the disclosure to its details.Unless otherwise indicated, all parts and percentages in the following examples and throughout the specification are by weight.

[0144] Examples

[0145] Preparation of Crosslinker 1. A blocked polyisocyanate crosslinker suitable for use in electrodepositable coating compositions was prepared in the following manner. Components 2 to 3 listed in Table 1 below were mixed in a flask set to total reflux while stirring under nitrogen. The mixture was heated to a temperature of 110°C, and component 1 was added dropwise such that the temperature increased due to the exothermic reaction and was maintained at 110°C. After the addition of component 1 was complete, component 4 was added to the heated reaction mixture. A temperature of 110°C was established in the reaction mixture, and the reaction mixture was maintained at that temperature until no residual isocyanate was detected by IR spectroscopy. Components 5 and 6 were then added and the reaction mixture was stirred for 30 minutes and cooled to ambient temperature.

[0146] Table 1. Components used to prepare crosslinker 1

[0147]

[0148]

[0149] 1 Rubinate M, available from Huntsman Corporation

[0150] 2 Dipropylene glycol monomethyl ether, available from Dow

[0151] 3 1-Methoxy-2-propanol, available from Dow

[0152] Preparation of Crosslinker 2. A blocked polyisocyanate crosslinker suitable for use in electrodepositable coating compositions was prepared in the following manner. Components 2 to 4 listed in Table 2 below were mixed in a flask set to total reflux while stirring under nitrogen. The mixture was heated to a temperature of 110°C, and component 1 was added dropwise such that the temperature increased due to the exothermic reaction and was maintained at 110°C. After the addition of component 1 was complete, component 5 was added to the heated reaction mixture. A temperature of 110°C was established in the reaction mixture, and the reaction mixture was maintained at that temperature until no residual isocyanate was detected by IR spectroscopy. Components 6 and 7 were then added and the reaction mixture was stirred for 30 minutes and cooled to ambient temperature.

[0153] Table 2. Components used to prepare crosslinker 2

[0154]

[0155] 1 Rubinate M, available from Huntsman Corporation

[0156] 21-methoxy-2-propanol, available from Dow

[0157] Preparation of a cationic amine functionalized polyepoxide based resin (Resin 1). A cationic amine functionalized polyepoxide based polymeric resin suitable for use in formulating an electrodepositable coating composition was prepared in the following manner. Components 1-4 listed in Table 3 below were combined in a flask set to full reflux under stirring with nitrogen. The mixture was heated to 130 °C and allowed to exotherm (up to 170 °C). A temperature of 145 °C was established in the reaction mixture, then the reaction mixture was held for 1.5 hours. Components 5-6 were then introduced to the reaction mixture, and a temperature of 100 °C was established in the reaction mixture. Components 7 and 8 were then added quickly to the reaction mixture, and the reaction mixture was allowed to exotherm. A temperature of 110 °C was established in the reaction mixture, and the reaction mixture was held for 1 hour. After the hold, the heat source was removed from the reaction mixture, and Component 9 was introduced slowly. The contents of the flask were stirred while cooling to room temperature. The resulting resin synthesis product I had a solids content of 86.9 wt.%.

[0158] Table 3. Components for preparing resin system 1

[0159]

[0160] 1 Epon 880, available from Hexion Corporation

[0161] 2 See above example crosslinker 1

[0162] 3 1-methoxy-2-propanol, available from Dow Chemical Company

[0163] Preparation of phosphate esterified acrylic polyol polymers A and B: Component 1 listed in Table 4 below was added to a flask set for full reflux under stirring with nitrogen and heated to 120 °C. Components 9 and 10 (initiator charge 1) were added dropwise to the flask over 3 hours and 35 minutes. Five minutes after the start of initiator charge 1, components 2-8 (monomer charge) were mixed in an addition funnel and added dropwise over 3.5 hours. Once the monomer charge was complete, charge 13 was used to rinse the monomer charge addition funnel. After both charges were complete, the reaction was held at 120 °C for 1 hour. Components 11 and 12 (initiator charge 2) were then added dropwise to the reaction flask through an addition funnel over 30 min. After the completion of initiator charge 2, component 14 was used to rinse the addition funnel. The reaction was held at 120 °C for 90 minutes and then cooled to room temperature with stirring. The resulting phosphate esterified acrylic polyol resin had a solids content of 56 wt.%.

[0164] Table 4. Components used to prepare phosphate esterified acrylic polyol polymers A and B

[0165]

[0166]

[0167] 1 Iboma, from Solvay

[0168] 2 Styrene, from Millipore Sigma

[0169] 3 2-Ethylhexyl acrylate, from Dow

[0170] 4 Tert-dodecyl mercaptan, from Arkema

[0171] 5 Each of PAM-100 and PAM-200 is a phosphoalkyl (meth)acrylate, obtained from Solvay Each of PAM-100 and PAM-200 is a phosphoalkyl (meth)acrylate, obtained from Solvay

[0172] 6 2-Hydroxyethyl acrylate, from BASF

[0173] 7 Hydroxy-functional methacrylate monomer, from Dow

[0174] 8 Luperox 575, from Arkema

[0175] Reference Electrophoretic Coating Preparation: The reference electrodepositable coating composition was prepared in the following manner. Components 1-6 listed in Table 4a below were combined in a stainless steel beaker and mixed under high shear (2500 RPM using a 1.5 inch Cowles blade powered by a Fawcett Model 103A air motor) starting at 40 °C for 5 minutes. The temperature was raised above 60 °C and maintained under the above mixing conditions for one hour after which the dispersion was determined with a Hegman gauge. A minimum reading of 5 must be achieved for adequate dispersion.

[0176] For the dispersion step, the mixture of components 7-8 was added to the clay / resin 1 paste. A temperature of less than 60°C was established, and the dispersion was mixed at 1500 RPM for one hour using a high-lift blade. After dispersion, the dispersion was cooled to ambient temperature, and component 9 was added to bring the final solids content of this dispersed paste to 50% by weight. Component 10 was then added to the dispersed formulation and mixed at ambient temperature for one hour to complete the feed at high solids. To produce the electrophoretic coating bath composition, the high-solids feed was further diluted to 25% by weight with component 11.

[0177] Table 4a. Components used to prepare reference electrophoretic coatings

[0178]

[0179] 1 ASP200 clay, available from BASF

[0180] 2 See above for example crosslinker 1

[0181] 3 See Example Resin System 1 above

[0182] 4 Dibutyltin dioxide paste, available from PPG Industries Inc.

[0183] Preparation of Electrophoretic Coating 1: An electrodepositable coating composition was prepared as follows. Components 1-6 listed in Table 4b below were combined in a stainless steel beaker and mixed under high shear (2500 RPM, using a 1.5-inch Cowles blade powered by a Fawcett 103A air motor) starting at 40°C for 5 minutes. The temperature was raised to above 60°C and the mixing conditions maintained for one hour, after which the dispersion was determined using a Hegman meter. A minimum reading of 5 was required for adequate dispersion.

[0184] For the dispersion step, the mixture of components 7-8 was added to the clay / resin 1 paste. A temperature of less than 60°C was established, and the dispersion was mixed at 1500 RPM for one hour using a high-lift blade. After dispersion, the dispersion was cooled to ambient temperature, and component 9 was added to bring the final solids content of this dispersed paste to 50% by weight. Component 10 was then added to the dispersed formulation and mixed at ambient temperature for one hour to complete the feed at high solids. To produce the electrophoretic coating bath composition, the high-solids feed was further diluted to 25% by weight with component 11.

[0185] Table 4b. Components used to prepare electrophoretic coating 1

[0186]

[0187] 1 ASP200 clay, available from BASF

[0188] 2 See above for example crosslinker 1

[0189] 3 See Example Resin System 1 above

[0190] 4 See Example Polymer A above

[0191] 5 Dibutyltin dioxide paste, available from PPG Industries Inc.

[0192] Preparation of Electrophoretic Coating 2: An electrodepositable coating composition was prepared as follows. Components 1-6, listed in Table 4c below, were combined in a stainless steel beaker and mixed under high shear (2500 RPM, using a 1.5-inch Cowles blade powered by a Fawcett Model 103A air motor) starting at 40°C for 5 minutes. The temperature was raised to above 60°C and the mixing maintained for one hour, after which the dispersion was determined using a Hegman meter. A minimum reading of 5 was required for adequate dispersion.

[0193] For the dispersion step, the mixture of components 7-8 was added to the clay / resin 1 paste. A temperature of less than 60°C was established, and the dispersion was mixed at 1500 RPM for one hour using a high-lift blade. After dispersion, the dispersion was cooled to ambient temperature, and component 9 was added to bring the final solids content of this dispersed paste to 40% by weight. Component 10 was then added to the dispersed formulation and mixed at ambient temperature for one hour to complete the feed at high solids. To produce the electrophoretic coating bath composition, the high-solids feed was further diluted to 25% by weight with component 11.

[0194] Table 4c. Components used to prepare electrophoretic coating 2

[0195] serial number Components Weight parts (g) 1 <![CDATA[板状颜料 1 ]]> 417.6 2 Crosslinker 2 2 ]]> 330.6 3 <![CDATA[树脂1 3 ]]> 389.3 4 <![CDATA[磷酸酯化丙烯酸多元醇聚合物A 4 ]]> 33.15 5 Phosphoric acid (85%) 5.55 6 Deionized water 76.2 7 Sulfamic acid 9.3 8 Deionized water 993.5 9 Deionized water 563.8 10 E6278 5 ]] 32.8 11 Deionized water 1691

[0196] 1 ASP200 clay, available from BASF

[0197] 2 See Example Crosslinker 2 above

[0198] 3 See Example Resin System 1 above

[0199] 4See Example Polymer A above

[0200] 5 Dibutyltin dioxide paste, available from PPG Industries Inc.

[0201] Evaluation of the compositions: Each test panel was immersed in the corresponding electrodepositable coating composition and electrodeposited using a DC powered rectifier (Xantrax Model XFR600-2, Elkhart, Indiana; or Sorensen Model XZG 300-5.6, Ameteck, Berwyn, Pennsylvania). The exact coating conditions and film formation for each coating are provided in the table below. After electrophoretic coating, each panel was rinsed with deionized water and baked in an electric oven (Despatch Model LFD-1-42) at 177°C.

[0202] condition Film formation (mil) 1.0 Voltage (V) 250 Current (amperes) 0.5 Time (minutes) 2 Baking time (minutes) 30

[0203] After baking, the electrophoretically coated panel was vertically scored on one side until the metal substrate. For corrosion performance evaluation, the panel was placed in a CASS (copper accelerated acetic acid salt spray) test for at least 21 minutes. At the end of the test, the panel was rated by measuring the paint loss (creep) caused by the scoring and the maximum creep (on both sides) of each panel in millimeters. After exposure, the corroded panel was dried under ambient conditions. The loose coating around the score was removed by applying Scotch tape (3MI Industries Adhesives and Tapes Divisions, St. Paul, Minnesota) and pulling it off. The width of the exposed metal area along the score was then recorded at 5 to 12 locations and averaged to evaluate the corrosion performance of the panel. As used herein, score creep refers to the paint loss area caused by corrosion or peeling (e.g., affected paint to affected paint) around the score. The panel under each condition was tested repeatedly, and the results were averaged. The results show that the score creep of the electrodeposited coating composition comprising a phosphated acrylic polyol polymer is improved, and are included in Table 5 below.

[0204] Table 5. Effect of Phosphated Polyols on Electrophoretic Coating Formulations

[0205]

[0206] Preparation of cationic amine functionalized polyepoxide-based resin (resin system 2). A cationic amine functionalized polyepoxide-based polymer resin suitable for formulating an electrodepositable coating composition was prepared in the following manner. Components 1-4 listed in Table 6 below were combined in a flask set to total reflux by stirring under nitrogen. The mixture was heated to 130°C and allowed to exotherm (maximum 170°C). A temperature of 145°C was established in the reaction mixture, and the reaction mixture was then kept 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 quickly added to the reaction mixture, and the reaction mixture was allowed to exotherm. A temperature of 110°C was established in the reaction mixture, and the reaction mixture was kept for 1 hour. After holding, the heat source was removed from the reaction mixture, and component 10 was slowly introduced. The contents of the flask were stirred while cooling to room temperature. The resulting resin synthesis product 2 had a solid content of 87.6% by weight.

[0207] Table 6. Components used to prepare resin system 2

[0208]

[0209] 1 Epon 880, available from Hexion Corporation

[0210] 2 See Example Cross-Linker 1 above.

[0211] 3 1-Methoxy-2-propanol, available from Dow Chemical Company

[0212] Preparation of Electrodepositable Coating Compositions: Electrodepositable coating compositions (Electrocoat Formulation A and Electrocoat Formulation B) were prepared as follows. Components 1-5 listed in Table 7 below were combined in a stainless steel beaker and mixed under high shear (2500 RPM, using a 1.5-inch Cowles blade powered by a Fawcett 103A air motor) starting at 40°C for 5 minutes. The temperature was raised to above 60°C and the mixing conditions were maintained for one hour, after which the degree of dispersion was determined using a Hegman meter. A minimum reading of 5 was required for adequate dispersion.

[0213] For the dispersion step, a mixture of components 6-7 was added to the clay / resin system I paste. A temperature of less than 60°C was established, and the dispersion was mixed at 1500 RPM for one hour using a high-lift blade. After dispersion, the dispersion was cooled to ambient temperature and component 8 was added. Component 9 was then added to the dispersed formulation and mixed at ambient temperature for one hour to complete the feed at high solids. To produce the electrophoretic coating bath composition, the high solids feed was further diluted with components 10-12.

[0214] Table 7. Components used to prepare reference electrophoretic coatings

[0215]

[0216] 1 See Example Resin System 3 above

[0217] 2 See Example Polymer A above

[0218] 3 ASP200 clay, available from BASF

[0219] 4 Dibutyltin dioxide paste, available from PPG Industries Inc.

[0220] 5 Hydroxylamine sulfate, available from Fisher Scientific

[0221] Evaluation of residence time and electrodeposition coatings

[0222] The CRS panels as described above were allowed to dwell in the electrodepositable coating composition and then the coating was electrodeposited. The coating conditions for Electrocoat Formulation A on flat steel are provided in Table 8 below.

[0223] Table 8: Coating conditions and thickness for flat panels

[0224] Electrophoretic coating formulations Dwell time before voltage application Temperature (F) Voltage coulomb A 15min 110 200V 35 A <0.5min 110 200V 35

[0225] To quantify whether a phosphate layer spontaneously deposits from an electrodepositable coating composition before the coating is electrodeposited, XRF measurements were performed on CRS panels remaining in the electrodepositable coating composition. For the XRF panels, the samples were immersed for the specified time, then rinsed with deionized water, and dried. The XRF measurements in Table 9 below were performed using a Hitachi X-MET 7500, and the counts corresponding to the phosphorus Ka peak at 2.01 kEV were measured after 30 seconds.

[0226] Table 9: XRF measurement results

[0227] Electrophoretic coating formulations Dwell time before voltage application Counting (2kEV) No - bare substrate none 103 A 15min 312

[0228] Immersing the CRS panels in the electrodepositable coating composition increased XRF counts compared to the bare CRS control, indicating that immersing the substrate caused a phosphorus layer to form on the substrate surface.

[0229] The electrophoretically coated test panels with and without extended dwell time before substrates were electrophoretically coated were evaluated by measuring the creep of the scribe from end to end after 500 hours of neutral salt spray exposure. At the end of the test, the panels were rated by measuring the coating loss (creep) caused by the scribe and the maximum creep (both sides) in millimeters of each panel. After exposure, the corroded panels were dried under ambient conditions. The loose coating around the scribe was removed by applying Scotch filament tape (3MI Industries Adhesives and Tapes Divisions, St. Paul, Minnesota) and tearing it off. The exposed metal areas of 5 to 12 positions were then recorded along the width of the scribe and averaged to evaluate the corrosion performance of the panel. As used herein, scribe creep refers to the paint loss area caused by corrosion or peeling (e.g., affected paint to affected paint) around the scribe. The panel under each condition was tested repeatedly, and the results were averaged. Compared to immediately electrophoretically coating the substrate with Formulation A, a significant reduction in scribe creep was observed with the extended dwell time prior to electrophoretic coating.

[0230] Table 10: 500-hour ASTM B117 scribe corrosion

[0231] Electrophoretic coating formulations Dwell time before voltage application Scribe creep (end to end) A 15min 4.5mm A 0min 10mm

[0232] To observe the effect on high surface area substrates, electrocoat formulation A was electrocoated onto 4 x 6 grit blasted panels (ACT Product No. 56225) having a thickness of 2.0 ± 0.5 mils according to the conditions in Table 11. The samples were allowed to dwell in the electrodepositable coating composition for a specific period of time before voltage was applied, and then voltage was applied to the electrocoated portion.

[0233] Table 11: Coating conditions and thickness of sandblasted panels

[0234]

[0235] To characterize surface corrosion, a 1-5 scale was used, where 1 corresponds to 75-100% corrosion, 2 corresponds to 50-75% corrosion, 3 corresponds to 25-50% corrosion, 4 corresponds to 10-25% corrosion, and 5 corresponds to <10% corrosion. The samples were subjected to neutral salt spray for 504 hours. As seen in Table 12 below, the e-coat formulation A with the immersion step significantly reduced surface corrosion compared to the e-coat alone.

[0236] Table 12: Neutral Salt Spray ASTM B117 504 hour face corrosion

[0237] Electrophoretic coating formulations Dwell time before voltage application B117 500 hours surface corrosion A 15min 5 A 0min 2

[0238] Evaluation of reverse polarity, current-assisted deposition, and electrodeposited coatings

[0239] In the current-assisted method, the CRS panels were immersed in the electrodepositable coating composition for a specific length of time while applying a low voltage anodic current. Table 13 below shows the XRF results after immersing the CRS panels in e-coat formulation A at 110 F for 4 minutes while applying a 10 volt voltage with the panels anodized. The XRF measurements were taken with a Hitachi X-MET 7500 and the counts at the 2.01 kEV peak corresponding to the phosphorous Ka peak were measured after rinsing and drying the panels with deionized water (Table 13).

[0240] Table 13: Current-assisted XRF measurements

[0241] Electrophoretic coating formulations Stay conditions Counting (2kEV) No - bare substrate none 103 A 4 minutes of anodic current assist (10 volts) 264

[0242] A significant increase in counts (phosphorous) was observed for the e-coat formulation A compared to the CRS control panels. Additionally, the use of a low voltage anodic current achieved an increase in phosphorous counts in a shorter amount of time compared to the dwell in the e-coat formulation without current.

[0243] To test the corrosion performance of the current-assisted method, 4 x 6 sandblasted panels (ACT product number 56225) with a thickness of 2.0 ± 0.5 mils were dwelled in the electrodepositable coating composition and a low voltage anodic current was applied to the part for a set amount of time. After applying the low voltage anodic current to the part, a higher voltage cationic current (referred to as cationic voltage in the tables below) was applied to the part in the same electrodepositable coating composition as the coating was applied. The exact conditions can be found in Table 14. The coating thickness was 40-50% of the sandblasted thickness. As in Example 1, a 1-5 corrosion scale was used. The samples were subjected to neutral salt spray for 504 hours. As seen in Table 15 below, the e-coat formulation A with the current-assisted step had reduced face corrosion compared to the e-coat application without a current-assisted dwell prior to coating.

[0244] Table 14: Current assisted sandblasted panel coating conditions and thickness

[0245]

[0246] Table 15: Neutral salt spray ASTM B117 504 hour face corrosion of current assisted panels

[0247] Evaluation of Phosphated Additives Using Residence Time or Current-Assisted Methods

[0248] In addition to utilizing phosphoric acid to obtain improved performance, phosphate functional polymers were incorporated into the electrodepositable coating compositions and the panels were treated in the electrodepositable coating composition by immersion or current assisted immersion processes prior to the application of cationic current to coat the parts. Sandblasted panel samples were prepared according to the conditions in Table 16 below.

[0249] Table 16: Coating conditions and thickness

[0250]

[0251] As in Example 1, a 1-5 corrosion rating was used. The samples were subjected to neutral salt spray for 504 hours. As seen in Table 17 below, the electrocoat formulation B with a current assisted step and an immersion step can greatly reduce face corrosion compared to an electrocoat only.

[0252] Table 17: Neutral salt spray ASTM B117 504 hours

[0253]

[0254] Those skilled in the art will appreciate that many modifications and variations are possible in light of the above teachings without departing from the broader scope of application described and exemplified herein. Accordingly, the intended scope of the application is not limited to the examples described herein but is intended to be limited only by the claims which follow and the full breadth of equivalents thereof.

Claims

1. A cationic electrodepositable coating composition comprising: An aromatic film-forming polymer containing a cationic salt group, wherein the amount of the aromatic film-forming polymer containing a cationic salt group is at least 10 wt %, such as at least 20 wt %, such as at least 30 wt %, such as at least 40 wt %, such as at least 50 wt %, such as at least 60 wt %, based on the total weight of the resin solids; an addition polymer comprising at least one phosphorylated group and optionally at least one hydroxyl functional group, wherein when the addition polymer comprises a (meth)acrylamide monomer, the addition polymer does not comprise a cationic or anionic salt group and the addition polymer comprises less than 60 wt.% of structural units comprising residues of hydroxyl functional (meth)acrylate monomers and / or hydroxyl functional (meth)acrylamide monomers, based on the total weight of the addition polymer; and Curing agent.

2. A cationic electrodepositable coating composition according to claim 1, wherein the aromatic film-forming polymer containing cationic salt groups is at least partially derived from a diglycidyl ether of a bisphenol.

3. A cationic electrodepositable coating composition according to any one of the preceding claims, wherein the addition polymer comprises the polymerization product of a monomer composition comprising: (a)C1-C 18 Alkyl (meth)acrylate monomers; and (b) Monomers containing phosphoric acid.

4. A cationic electrodepositable coating composition comprising: Film-forming polymers containing cationic salt groups; An addition polymer comprising the polymerization product of a monomer composition comprising: (a)C1-C 18 Alkyl (meth)acrylate monomers; and (b) phosphoric acid-containing monomers, wherein when the addition polymer comprises a (meth)acrylamide monomer, the addition polymer does not comprise cationic or anionic salt groups and the addition polymer comprises less than 60 wt. % of structural units comprising residues of hydroxy-functional (meth)acrylate monomers and / or hydroxy-functional (meth)acrylamide monomers, based on the total weight of the addition polymer; and Curing agent.

5. The cationic electrodepositable coating composition of any one of the preceding claims, wherein the monomer composition further comprises at least one of: (c) hydroxy-functional (meth)acrylate monomers; (d) vinyl aromatic compounds; (e) monomers containing two or more ethylenically unsaturated groups per molecule; (f) alkyl(meth)acrylamide monomers; and / or (g) Hydroxy-functional (meth)acrylamide monomer.

6. A cationic electrodepositable coating composition comprising: Film-forming polymers containing cationic salt groups; A polymer comprising at least one phosphorylated group and optionally at least one hydroxyl functional group, wherein when the polymer comprises a (meth)acrylamide monomer, the polymer does not comprise a cationic or anionic salt group and the polymer comprises less than 60 wt.% of structural units comprising residues of hydroxyl functional (meth)acrylate monomers and / or hydroxyl functional (meth)acrylamide monomers, based on the total weight of the polymer; curing agent; and Pigment, wherein the pigment to binder ratio is greater than 0.5:1, such as at least 0.60:1, such as greater than 0.67:1, such as at least 0.70:1, 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, and / or wherein the pigment comprises an inorganic plate-like pigment, wherein the inorganic plate-like pigment to binder ratio is at least 0.4:1, such as at least 0.5:1, such as at least 0.60:1, such as at least 0.70:1, 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.

7. A cationic electrodepositable coating composition according to any one of the preceding claims, wherein the addition polymer is present in an amount of 0.01 wt% to 50 wt%, based on the total weight of resin solids in the cationic electrodepositable coating composition.

8. A cationic electrodepositable coating composition according to any one of preceding claims 3 to 7, wherein the phosphoric acid-containing monomer is present in the monomer composition in an amount of 0.1 wt% to 20 wt%, based on the total weight of the monomer composition.

9. A cationic electrodepositable coating composition according to any one of the preceding claims, wherein the addition polymer comprises hydroxyl functional groups and has a hydroxyl value of from 1 mg KOH / g to 500 mg KOH / g addition polymer.

10. A cationic electrodepositable coating composition according to any one of the preceding claims, wherein the addition polymer has a phosphoric acid equivalent weight of 0.01 to 10 milliequivalents per gram of addition polymer.

11. A cationic electrodepositable coating composition comprising: Film-forming polymers containing cationic salt groups; Phosphated epoxy resin; and Curing agent.

12. The cationic electrodepositable coating composition of claim 11, wherein the phosphated epoxy resin is present in an amount of 0.01 wt% to 50 wt% based on the total weight of resin solids in the cationic electrodepositable coating composition.

13. A cationic electrodepositable coating composition according to any one of the preceding claims 11 or 12, wherein the phosphated epoxy resin has a phosphoric acid equivalent weight of 0.01 to 10 milliequivalents per gram of phosphated epoxy resin.

14. A cationic electrodepositable coating composition according to any one of the preceding claims 11 to 13, wherein the phosphated epoxy resin has a hydroxyl value of 1 mg KOH / g to 600 mg KOH / g.

15. A method of coating a metal substrate, comprising: (1) Immersing the surface of the metal substrate to be coated into a cationic electrodepositable coating composition, wherein the cationic electrodepositable coating composition comprises: (a) a film-forming polymer containing a cationic salt group; (b) a curing agent; and (c) a source of phosphate ions or a polymer comprising at least one phosphated group, wherein the metal substrate serves as a cathode in electrical communication with an anode immersed in the cationic electrodepositable coating composition; (2) allowing the immersed metal substrate to reside in the cationic electrodepositable coating composition for a period of time, thereby forming a metal phosphate layer over at least a portion of the surface of the metal substrate; and (3) applying a direct current between the cathode and the anode, thereby depositing the cationic electrodepositable coating composition on the surface of the metal substrate to form a coating.

16. The method of claim 15, wherein the metal substrate is not treated with a pretreatment composition prior to immersion in the cationic electrodepositable coating composition.

17. A method of coating a metal substrate, comprising: (1) Immersing the surface of the metal substrate to be coated into a cationic electrodepositable coating composition, wherein the cationic electrodepositable coating composition comprises: (a) a film-forming polymer containing a cationic salt group; (b) a curing agent; and (c) a source of phosphate ions or a polymer comprising at least one phosphated group, wherein the metal substrate serves as an electrode in electrical communication with a counter electrode immersed in the cationic electrodepositable coating composition; (2) applying a direct current between the electrode and the counter electrode, wherein the electrode serves as an anode and the counter electrode serves as a cathode, thereby forming a metal phosphate layer on at least a portion of the surface of the metal substrate; as well as (3) applying a direct current between the electrode and the counter electrode, wherein the polarity is reversed and the electrode functions as a cathode and the counter electrode functions as an anode, thereby depositing the cationic electrodepositable coating composition on the surface of the metal substrate to form a coating.

18. The method of claim 17, wherein the metal substrate is not treated with a pretreatment composition prior to immersion in the cationic electrodepositable coating composition.

19. A method of coating a metal substrate, comprising: (1) Immersing the surface of the metal substrate to be coated into a cationic electrodepositable coating composition, wherein the cationic electrodepositable coating composition comprises: (a) a film-forming polymer containing a cationic salt group; (b) a curing agent; and (c) a source of phosphate ions or a polymer comprising at least one phosphated group, wherein the metal substrate serves as an electrode in electrical communication with a counter electrode immersed in the cationic electrodepositable coating composition; as well as (2) applying a direct current between the electrode and the counter electrode, thereby depositing the cationic electrodepositable coating composition on the surface of the metal substrate to form a coating; wherein the metal substrate is not treated with a pretreatment composition prior to being immersed in the cationic electrodepositable coating composition.

20. The method of any one of claims 15 to 19, wherein the cationic electrodepositable coating composition comprises any one of the cationic electrodepositable coating compositions of claims 1 to 14.

21. A coated substrate coated with a coating deposited from the electrodepositable coating composition of any one of claims 1 to 14.

22. A coated substrate coated by the method according to any one of claims 15 to 20.

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