ELECTRODEPOSITABLE COATING COMPOSITIONS

Abstract

The present invention relates to an electrodepositable coating composition comprising an acrylic polymer comprising more than 60% by weight of constituent units comprising the residue of a hydroxyl-functional (meth)acrylate monomer and / or a hydroxyl-functional (meth)acrylamide monomer, depending on the total weight of the acrylic polymer; and a film-forming polymer containing an ionic salt group different from the acrylic polymer. Coatings, coated substrates, and methods for coating a substrate are also disclosed.

Description

ELECTRODEPOSITABLE COATING COMPOSITIONS FIELD OF INVENTION

[0001] The present invention relates to an electrodepositable coating composition, treated substrates, and methods of coating substrates. BACKGROUND OF THE INVENTION

[0002] Electrodeposition as a coating application method involves the deposition of a film-forming composition onto a conductive substrate under the influence of an applied electrical potential. Electrodeposition gained popularity in the coatings industry because it provides greater paint utilization, excellent corrosion resistance, and low environmental pollution compared to non-electrophoretic coating methods. Both cationic and anionic electrodeposition processes are used commercially. One problem associated with electrodeposition as practiced industrially is coverage over the edges of the substrate being coated. The coating is relatively thin (i.e., low film thickness) in these edge areas. Additionally, coatings tend to sag away from sharp edges and corners due to the higher surface energy required to hold the coating in place.The problems tend to result in early and severe corrosion at the edge.

[0003] Therefore, an electrodepositable coating composition that provides improved edge coverage is desirable. BRIEF DESCRIPTION OF THE INVENTION

[0004] The present invention provides an electrodepositable coating composition comprising (a) an acrylic polymer greater than 60 wt% of constitutional units comprising the residue of a hydroxyl-functional (meth)acrylate monomer and / or a hydroxyl-functional (meth)acrylamide monomer, depending on the total weight of the acrylic polymer; and (b) a film-forming polymer containing an ionic salt group different from the acrylic polymer.

[0005] The present invention also provides a method for coating a substrate comprising electrophoretically applying a coating deposited from an electrodepositable coating composition of the present invention onto at least a portion of the substrate.

[0006] The present invention further provides a coating deposited from an electrodepositable coating composition comprising (a) an acrylic polymer comprising more than 60% by weight of constitutional units comprising the residue of a hydroxyl-functional (meth)acrylate monomer and / or a hydroxyl-functional (meth)acrylamide monomer, depending on the total weight of the acrylic polymer; and (b) a film-forming polymer containing an ionic salt group different from the acrylic polymer.

[0007] The present invention further provides a substrate coated with a coating deposited from the electrodepositable coating composition of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0008] The present invention relates to an electrodepositable coating composition comprising an acrylic polymer comprising more than 60% by weight of constitutional units comprising the residue of a hydroxyl-functional (meth)acrylate monomer and / or a hydroxyl-functional (meth)acrylamide monomer; and a film-forming polymer containing an ionic salt group different from the acrylic polymer.

[0009] According to the present invention, the expression electrodepositable coating composition refers to a composition that is capable of being deposited on an electrically conductive substrate under the influence of an applied electric potential. Acrylic polymer

[0010] According to the present invention, the electrodepositable coating compositions of the present invention may comprise an acrylic polymer comprising more than 60% by weight of constituent units comprising the residue of a hydroxyl-functional (meth)acrylate monomer and / or a hydroxyl-functional (meth)acrylamide monomer, based on the total weight of the acrylic polymer. As used herein, the term acrylic polymer refers to a polymerization product comprising at least partially constituent units comprising the residue of (meth)acrylic monomers and / or (meth)acrylamide monomers, and the acrylic polymer of the present invention comprises more than 60% by weight of constituent units comprising the residue of a hydroxyl-functional (meth)acrylate monomer and / or a hydroxyl-functional (meth)acrylamide monomer, based on the total weight of the acrylic polymer.As used herein, the term (meth)acrylate and similar terms are intended to include both acrylates and methacrylates. As used herein, the term (meth)acrylamide and similar terms encompass both acrylamides and methacrylamides. As used herein, the expression "constitutional unit comprising the residue of" refers to a part of the acrylic polymer structure that corresponds to the residue of an individual monomer following polymerization.

[0011] The hydroxyl-functional (meth)acrylate monomer may comprise a hydroxyalkyl (meth)acrylate, such as, for example, a Ci to C1o hydroxyalkyl (meth)acrylate, such as a Ci to C2s hydroxyalkyl (meth)acrylate, such as a Ci to C3 hydroxyalkyl (meth)acrylate. Non-limiting examples of hydroxyalkyl (meth)acrylate monomers include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, and the like, as well as combinations thereof. The hydroxyl-functional (meth)acrylate monomer comprises a primary hydroxyl group, secondary hydroxyl groups, a tertiary hydroxyl group, or combinations thereof.The constitutional units comprising the hydroxyl-functional (meth)acrylate residue may be present in the acrylic polymer in an amount of at least 61% by weight, such as at least 70% by weight, such as at least 80% by weight, such as at least 90% by weight, such as at least 93% by weight, such as at least 95% by weight, such as at least 97% by weight, such as at least 100% by weight, based on the total weight of the acrylic polymer. The constitutional units comprising the residue of the hydroxyfunctional (meth)acrylate may be present in the acrylic polymer in an amount of not more than 100% by weight, such as not more than 97% by weight, such as not more than 95% by weight, such as not more than 90% by weight, such as not more than 85% by weight, such as not more than 75% by weight, such as not more than 70% by weight, based on the total weight of the acrylic polymer.The constitutional units comprising the hydroxyl-functional (meth)acrylate residue may be present in the acrylic polymer in an amount of 61% to 100% by weight, such as 70% to 100% by weight, such as 80% to 100% by weight, such as 90% to 100% by weight, such as 93% to 100% by weight, such as 95% to 100% by weight, such as 97% to 100% by weight, such as 61% to 97% by weight, such as 70% to 97% by weight, such as 80% to 97% by weight, such as 90% to 97% by weight, such as 93% to 97% by weight, such as 95% to 97% by weight, such as 61% to 95% by weight, such as 70% to 95% by weight, such as 80% to 95% by weight, such as 90% to 95% by weight, such as 93% to 95% by weight, such as 61% to 90% by weight, such as 70% to 90% by weight, such as 80% to 90% by weight, 61% to 85% by weight, such as 70% to 85% by weight, such as 80% to 85% by weight, 61% to 75% by weight, such as 70% to 75% by weight, such as 61% to 70% by weight, based on the total weight of the acrylic polymer.

[0012] The hydroxyl-functional (meth)acrylamide monomer may comprise a hydroxyalkyl (meth)acrylamide, such as, for example, a C1 to C10 hydroxyalkyl (meth)acrylamide, such as a C1 to C5 hydroxyalkyl (meth)acrylamide, such as a C1 to C3 hydroxyalkyl (meth)acrylamide. Non-limiting examples of hydroxyalkyl (meth)acrylamide monomers include hydroxymethyl (meth)acrylamide, hydroxyethyl (meth)acrylamide, and the like, as well as combinations thereof. The hydroxyl-functional (meth)acrylamide monomer comprises a primary hydroxyl group, secondary hydroxyl groups, a tertiary hydroxyl group, or combinations thereof.The constitutional units comprising the hydroxyl-functional (meth)acrylamide residue may be present in the acrylic polymer in an amount of at least 61% by weight, such as at least 70% by weight, such as at least 80% by weight, such as at least 90% by weight, such as at least 93% by weight, such as at least 95% by weight, such as at least 97% by weight, such as at least 100% by weight, based on the total weight of the acrylic polymer. The constitutional units comprising the hydroxyl-functional (meth)acrylamide residue may be present in the acrylic polymer in an amount of not more than 100% by weight, such as not more than 97% by weight, such as not more than 95% by weight, such as not more than 90% by weight, such as not more than 85% by weight, such as not more than 75% by weight, such as not more than 70% by weight, based on the total weight of the acrylic polymer.The constitutional units comprising the hydroxyl-functional (meth)acrylamide residue may be present in the acrylic polymer in an amount of 61% to 100% by weight, such as 70% to 100% by weight, such as 80% to 100% by weight, such as 90% to 100% by weight, such as 93% to 100% by weight, such as 95% to 100% by weight, such as 97% to 100% by weight, such as 61% to 97% by weight, such as 70% to 97% by weight, such as 80% to 97% by weight, such as 90% to 97% by weight, such as 93% to 97% by weight, such as 95% to 97% by weight, such as 61% to 95% by weight, such as 70% to 95% by weight, such as 80% to 95% by weight, such as 90% to 95% by weight, such as 93% to 95% by weight, such as 61% to 90% by weight, such as 70% to 90% by weight, such as 80% to 90% by weight, 61% to 85% by weight, such as 70% to 85% by weight, such as 80% to 85% by weight, 61% to 75% by weight, such as 70% to 75% by weight, such as 61% to 70% by weight, based on the total weight of the acrylic polymer.

[0013] The acrylic polymer may further optionally comprise constitutional units comprising residues of unsaturated monomers not containing hydroxyl. For example, the acrylic polymer may further optionally comprise constitutional units comprising residues of alkyl (meth)acrylates, aromatic vinyl compounds, ethylenically unsaturated epoxide-functional monomers, ethylenically unsaturated acid-functional monomers, monomers comprising two or more ethylenically unsaturated groups per molecule, ethylenically unsaturated amide-functional monomers, ethylenically unsaturated carbamate-functional monomers, and ethylenically unsaturated thiol-functional monomers, and combinations thereof.The constituent units comprising the residue of such monomer may comprise no more than 39% by weight of the acrylic polymer, such as no more than 25% by weight, such as no more than 15% by weight, such as no more than 10% by weight, such as no more than 7% by weight, such as no more than 5% by weight, such as no more than 3% by weight, based on the total weight of the acrylic polymer. Alternatively, the acrylic polymer may be substantially free, essentially free, or completely free of such monomers.

[0014] The acrylic polymer may further optionally comprise constitutional units comprising residues of alkyl (meth)acrylates such as Ci-Cis alkyl (meth)acrylates. Examples of suitable Ci-Cis 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, as well as combinations thereof. The constitutional units comprising the residue of Ci-Cie alkyl (meth)acrylates may be present in the acrylic polymer in an amount of up to 39% by weight, such as 1% to 30% by weight, such as 1% to 20% by weight, such as 1% to 10% by weight, such as 2% to 8% by weight, such as 3% to 6% by weight, depending on the total weight of the acrylic polymer.

[0015] The acrylic polymer may further optionally comprise constitutional units comprising the residue of an ethylenically unsaturated amino-functional monomer. The ethylenically unsaturated amino-functional monomer may comprise, for example, 2-(dimethylamino)ethyl methacrylate (DMAEMA), 2-(dimethylamino)ethyl acrylate, 3-(dimethylamino)propyl (meth)acrylate, 2-(diethylamino)ethyl (meth)acrylate, 2-(tert-butylamino)ethyl (meth)acrylate, and 2-(diethylamino)ethyl (meth)acrylate, as well as combinations thereof. The constitutional units comprising the amino-functional monomer residue may be present in the acrylic polymer, if at all, in an amount of up to 39% by weight, such as 1% to 30% by weight, such as 1% to 20% by weight, such as 1% to 10% by weight, such as 2% to 8% by weight, such as 3% to 6% by weight, depending on the total weight of the acrylic polymer.The use of an ethylenically unsaturated amino-functional monomer in the polymerization of an acrylic polymer can produce an acrylic polymer comprising amino-functional groups. Consequently, the acrylic polymer may optionally comprise amino-functional groups.

[0016] The acrylic polymer may optionally further comprise constitutional units comprising the residue of an aromatic vinyl compound. Non-limiting examples of suitable aromatic vinyl compounds include styrene, alpha-methylstyrene, alpha-chloromethylstyrene, and / or vinyl toluene, as well as combinations thereof. The constitutional units comprising the residue of the aromatic vinyl compound may be present in the acrylic polymer in an amount up to 39% by weight, such as from 1% to 30% by weight, such as from 1% to 20% by weight, such as 1% to 10% by weight, such as 2% to 8% by weight, such as 3% to 6% by weight, depending on the total weight of the acrylic polymer.

[0017] The acrylic polymer may further optionally comprise constitutional units comprising the residue of an ethylenically unsaturated epoxide-functional monomer. Examples of suitable ethylenically unsaturated epoxide-functional monomers include glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl(meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl(meth)acrylate, or allyl glycidyl ether. The constitutional units comprising the ethylene-unsaturated epoxide-functional monomer residue may be present in the acrylic polymer, if at all, in an amount of up to 39% by weight, such as 1% to 30% by weight, such as 1% to 20% by weight, such as 1% to 10% by weight, such as 2% to 8% by weight, such as 3% to 6% by weight, depending on the total weight of the acrylic polymer.The use of an ethylenically unsaturated epoxide-functional monomer in the polymerization of an acrylic polymer can produce an acrylic polymer comprising epoxide-functional groups. Consequently, the acrylic polymer may optionally comprise epoxide-functional groups.

[0018] The acrylic polymer may optionally further comprise constitutional units comprising the residue of an ethylenically unsaturated acid-functional monomer. The ethylenically unsaturated acid-functional monomer may comprise ethylenically unsaturated phosphoric acid-functional or carboxylic acid-functional monomers, such as, for example, (meth)acrylic acid. The constitutional units comprising the acid-functional monomer residue may be present in the acrylic polymer, if present, in an amount of up to 39% by weight, such as 1% to 30% by weight, such as 1% to 20% by weight, such as 1% to 10% by weight, such as 2% to 8% by weight, or such as 3% to 6% by weight, depending on the total weight of the acrylic polymer. The use of an ethylenically unsaturated acid-functional monomer in the polymerization of the acrylic polymer may produce an acrylic polymer comprising acid-functional groups.Consequently, the acrylic polymer may optionally comprise acid-functional groups.

[0019] The acrylic polymer may further optionally comprise constitutional units comprising a monomer residue comprising two or more ethylenically unsaturated groups per molecule, such as a monomer comprising three or more ethylenically unsaturated groups. Examples of suitable monomers having two ethylenically unsaturated groups per molecule include ethylene glycol dimethacrylate, allyl methacrylate, hexanediol diacrylate, methacrylic anhydride, tetraethylene glycol diacrylate, and / or tripropylene glycol diacrylate. Examples of monomers having three or more ethylenically unsaturated groups per molecule include ethoxylated trimethylolpropane triacrylate having 0 to 20 ethoxy units, [ethoxylated] trimethylolpropane trimethacrylate having 0 to 20 ethoxy units, di-pentaerythritol triacrylate, pentaerythritol tetraacrylate and / or di-pentaerythritol pentaacrylate.The constituent units comprising the monomer residue containing two or more ethylenically unsaturated groups per molecule may be present in the acrylic polymer in an amount of up to 15% by weight, such as from 0.1% to 10% by weight, or from 0.1% to 5% by weight, depending on the total weight of the acrylic polymer. The use of a monomer comprising two or more ethylenically unsaturated groups per molecule in the polymerization of the acrylic polymer may produce an acrylic polymer comprising ethylenically unsaturated groups. Accordingly, the acrylic polymer may optionally comprise ethylenically unsaturated groups.

[0020] The acrylic polymer may optionally further comprise constitutional units comprising the residue of an ethylenically unsaturated amide-functional monomer that does not include a hydroxyl group. Examples of ethylenically unsaturated amide-functional monomers include acrylamide, (meth)acrylamide, and substituted N-alkyl (meth)acrylamides. The constitutional units comprising the ethylenically unsaturated amide-functional monomer residue may be present in the acrylic polymer in an amount of up to 39% by weight, such as 1% to 30% by weight, 1% to 20% by weight, 1% to 10% by weight, 2% to 8% by weight, or 3% to 6% by weight, depending on the total weight of the acrylic polymer. The use of an ethylenically unsaturated amide-functional monomer in the polymerization of the acrylic polymer can produce an acrylic polymer comprising amide-functional groups.Consequently, the acrylic polymer may optionally comprise amide-functional groups.

[0021] The acrylic polymer may optionally further comprise constitutional units comprising the residue of other ethylenically unsaturated hydroxyl-functional monomers that are not (meth)acrylates or (meth)acrylamides. Examples of ethylenically unsaturated hydroxyl-functional monomers include vinyl alcohol and the like. The constitutional units comprising the residue of the ethylenically unsaturated hydroxyl-functional monomers that are not (meth)acrylates or (meth)acrylamides may be present in the acrylic polymer in an amount of up to 39% by weight, such as 1% to 30% by weight, such as 1% to 20% by weight, such as 1% to 10% by weight, such as 2% to 8% by weight, such as 3% to 6% by weight, depending on the total weight of the acrylic polymer.

[0022] Alternatively, the acrylic polymer may be substantially free, essentially free, or completely free of the constituent units comprising the vinyl alcohol residue. As used herein, the acrylic polymer is substantially free of constituent units comprising the vinyl alcohol residue if the constituent units comprising the vinyl alcohol residue are present in the acrylic polymer, if at all, in an amount of less than 3% by weight, based on the total weight of the acrylic polymer. As used herein, the acrylic polymer is essentially free of constituent units comprising the vinyl alcohol residue if the constituent units comprising the vinyl alcohol residue are present in the acrylic polymer, if at all, in an amount of less than 1% by weight, based on the total weight of the acrylic polymer.As used herein, the acrylic polymer is completely free of constitutional units comprising vinyl alcohol residue if the constitutional units comprising vinyl alcohol residue are present in the acrylic polymer, i.e., 0% by weight.

[0023] Acrylic polymer may be substantially free, essentially free, or completely free of the constituent units comprising nitrogen-containing monomer residue. As used herein, acrylic polymer is substantially free of constituent units comprising nitrogen-containing monomer residue if the constituent units comprising nitrogen-containing monomer residue are present in the acrylic polymer, if at all, in an amount of less than 3% by weight, based on the total weight of the acrylic polymer.As used herein, the acrylic polymer is essentially free of constituent units comprising nitrogen-containing monomer residue if such constituent units are present in the acrylic polymer, if at all, in an amount of less than 1% by weight, based on the total weight of the acrylic polymer. As used herein, the acrylic polymer is completely free of constituent units comprising nitrogen-containing monomer residue if such constituent units are not present in the acrylic polymer, i.e., 0% by weight.

[0024] The acrylic polymer of the present invention may be substantially free, essentially free, or completely free of the constituent units comprising the residue of a polymeric dispersant. As used herein, the acrylic polymer is substantially free of constituent units comprising the residue of a polymeric dispersant if the constituent units comprising the residue of the polymeric dispersant are present in the acrylic polymer, if present, in an amount of less than 15% by weight, based on the total weight of the acrylic polymer. As used herein, the acrylic polymer is essentially free of constituent units comprising the residue of a polymeric dispersant if the constituent units comprising the residue of the polymeric dispersant are present in the acrylic polymer, if present, in an amount of less than 5% by weight, based on the total weight of the acrylic polymer.As used herein, the acrylic polymer is completely free of constitutional units comprising the residue of a polymeric dispersant if the constitutional units comprising the residue of polymeric dispersant are not present in the acrylic polymer, i.e., 0% by weight.

[0025] The acrylic polymer of the present invention comprises active hydrogen functional groups. As used herein, the term active hydrogen functional groups refers to those groups that are reactive with isocyanates as determined by the Zerewitinoff test as described in the JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 49, page 3181 (1927). Active hydrogen functional groups may include hydroxyl groups, thiol groups, amide groups, carbamate groups, primary amino groups, and / or secondary amino groups.

[0026] According to the present invention, the acrylic polymer may have a theoretical hydroxyl equivalent weight of at least 100 g / hydroxyl group (OH), such as at least 110 g / OH, such as at least 120 g / OH, such as at least 140 g / OH, and may be no greater than 500 g / OH, such as no greater than 400 g / OH, such as no greater than 300 g / OH, such as no greater than 200 g / OH, such as no greater than 150 g / OH, such as no greater than 140 g / OH, such as no greater than 130 g / OH.The acrylic polymer can have a theoretical hydroxyl equivalent weight of 100 g / OH to 500 g / OH, such as 100 g / OH to 400 g / OH, such as 100 g / OH to 300 g / OH, such as 100 g / OH to 200 g / OH, such as 100 g / OH to 150 g / OH, such as 100 g / OH to 140 g / OH, such as 100 g / OH to 130 g / OH, such as 110 g / OH to 500 g / OH, such as 110 g / OH to 400 g / OH, such as 110 g / OH to 300 g / OH, such as 110 g / OH to 200 g / OH, such as 110 g / OH to 150 g / OH, such as 110 g / OH to 140 g / OH, such as from 110 g / OH to 130 g / OH, such as from 120 g / OH to 500 g / OH, such as from 120 g / OH to 400 g / OH, such as from 120 g / OH to 300 g / OH, such as from 120 g / OH to 200 g / OH, such as from 120 g / OH to 150 g / OH, such as from 120 g / OH to 140 g / OH, such as from 120 g / OH to 130 g / OH, such as from 140 g / OH to 500 g / OH, such as from 140 g / OH to 400 g / OH, such as from 140 g / OH to 300 g / OH, such as from 140 g / OH to 200 g / OH, such as from 140 g / OH to 150 g / OH.As used herein, the expression theoretical hydroxyl equivalent weight refers to the weight in grams of acrylic polymer resin solids divided by the theoretical equivalents of the hydroxyl groups present in the acrylic polymer resin, and can be calculated according to the following formula (1):. Total grams of acrylic polymer resin solids (1) Hydroxyl equivalent weight = -----------Theoretical equivalents of OH-----------

[0027] According to the present invention, the acrylic polymer may have a theoretical hydroxyl value of at least 100 mg KOH / gram of acrylic polymer, such as at least 250 mg KOH / gram of acrylic polymer, such as at least 400 mg KOH / gram of acrylic polymer, such as at least 450 mg KOH / gram of acrylic polymer and may be no greater than 500 mg KOH / gram of acrylic polymer, such as no greater than 600 mg KOH / gram of acrylic polymer, such as no greater than 560 mg KOH / gram of acrylic polymer, such as no greater than 500 mg KOH / gram of acrylic polymer, such as not greater than 400 mg KOH / gram of acrylic polymer, such as not greater than 300 mg KOH / gram of acrylic polymer. The acrylic polymer can have a theoretical hydroxyl value of 100 to 600 mg KOH / gram of acrylic polymer, such as 250 to 600 mg KOH / gram of acrylic polymer, such as 400 to 600 mg KOH / gram of acrylic polymer, such as 500 to 600 mg KOH / gram of acrylic polymer, such as 100 to 500 mg KOH / gram of acrylic polymer, such as 250 to 500 mg KOH / gram of acrylic polymer, such as 400 to 500 mg KOH / gram of acrylic polymer, 100 to 400 mg KOH / gram of acrylic polymer, such as 250 to 400 mg KOH / gram of acrylic polymer, 100 to 300 mg KOH / gram of acrylic polymer, such as 250 to 300 mg KOH / gram of acrylic polymer.As used herein, the expression theoretical hydroxyl value refers to the amount of milligrams of potassium hydroxide required to neutralize the acetic acid absorbed in the acetylation of one gram of a chemical containing free hydroxyl groups, and herein was determined by a theoretical calculation of the amount of free hydroxyl groups theoretically present in one gram of the acrylic polymer.

[0028] According to the present invention, the acrylic polymer may have an average molecular weight at z (Mz) of at least 500,000 g / mol, such as at least 1,000,000 g / mol, such as at least 1,400,000 g / mol, such as at least 1,750,000 g / mol, such as at least 2,000,000 g / mol, such as at least 2,500,000. The acrylic polymer may have an average molecular weight at z (Mz) of no more than 600,000,000 g / mol, such as no more than 60,000,000 g / mol, such as no more than 50,000,000 g / mol, such as no more than 35,000,000 g / mol, such as no more than 20,000,000 g / mol, such as no more than 10,000,000 g / mol, such as no more than 7,000,000 g / mol, such as no more than 5,000,000 g / mol, such as no more than 4,000,000 g / mol, such as no more than 3,500,000 g / mol, such as no more than 3,000,000. The acrylic polymer can have an average molecular weight at z of 500,000 to 600,000,000 g / mol, such as 500,000 to 60,000,000 g / mol, such as 500,000 to 50,000,000 g / mol, such as 500,000 to 35,000,000 g / mol, such as 500,000 to 20,000,000 g / mol, such as 500,000 to 10,000,000 g / mol, such as 500,000 to 4,000,000 g / mol, such as 500,000 to 3,500,000 g / mol, such as 500,000 to 3,000,000 g / mol, such as 1,000,000 to 600,000,000 g / mol, such as 1,000,000 to 60,000,000 g / mol, such as 1,000,000 to 50,000,000 g / mol, such as 1,000,000 to 35,000,000 g / mol, such as 1,000,000 to 20,000,000 g / mol, such as 1,000,000 to 10,000,000 g / mol, such as 1,000,000 to 4,000,000 g / mol, such as 1,000,000 to 3,500,000 g / mol, such as 1,000,000 to 3,000,000 g / mol, such as 1,400,000 to 600,000,000 g / mol, such as 1,400,000 to 60,000,000 g / mol, such as 1,400,000 to 50,000,000 g / mol, such as 1,400,000 to 35,000,000 g / mol, such as 1,400,000 to 20,000,000 g / mol, such as 1,400,000 to 10,000,000 g / mol, such as 1,400,000 to 4,000,000 g / mol, such as 1,400,000 to 3,500,000 g / mol, such as 1,400,000 to 3,000,000 g / mol, such as 1,750,000 to 600,000,000 g / mol, such as 1,750,000 to 60,000,000 g / mol, such as 1,750,000 to 50,000,000 g / mol, such as 1,750,000 to 35,000,000 g / mol, such as μλ / t / zuzz / uzo ι yy, 1,750,000 to 20,000,000 g / mol, such as 1,750,000 to 10,000,000 g / mol, such as 1,750,000 to 4,000,000 g / mol, such as 1,750,000 to 3,500,000 g / mol, such as 1,750,000 to 3,000,000 g / mol, such as 2,000,000 to 600,000,000 g / mol, such as 2,000,000 to 60,000,000 g / mol, such as 2,000,000 to 50,000,000 g / mol, such as 2,000,000 to 35,000,000 g / mol, such as 2,000,000 to 20,000,000 g / mol, such as 2,000,000 to 10,000,000 g / mol, such as 2,000,000 to 4,000,000 g / mol, such as 2,000,000 to 3,500,000 g / mol, such as 2,000,000 to 3,000,000 g / mol, such as 2,500,000 to 600,000,000 g / mol, such as 2,500,000 to 60,000,000 g / mol, such as 2,500,000 to 50,000,000 g / mol, such as 2,500,000 to 35,000,000 g / mol, such as 2,500,000 to 20,000,000 g / mol, such as 2,500,000 to 10,000,000 g / mol, such as 2,500,000 to 4,000,000 g / mol, such as 2,500,000 to 3,500,000 g / mol, such as 2,500,000 to 3,000,000 g / mol.

[0029] According to the present invention, the acrylic polymer may have a weight average molecular weight (Mw) of at least 200,000 g / mol, such as at least 400,000 g / mol, such as at least 500,000 g / mol and may have a weight average molecular weight of no more than 1,600,000 g / mol, such as no more than 1,200,000 g / mol, such as no more than 1,100,000 g / mol, such as no more than 900,000 g / mol, such as no more than 800,000 g / mol.According to the present invention, the acrylic polymer can have a weight average molecular weight of 200,000 to 1,600,000 g / mol, such as 200,000 to 1,200,000 g / mol, such as 200,000 to 1,100,000 g / mol, such as 200,000 to 900,000 g / mol, such as 200,000 to 800,000 g / mol, such as 400,000 to 1,600,000 g / mol, such as 400,000 to 1,200,000 g / mol, such as 400,000 to 1,100,000 g / mol, such as 400,000 to 900,000 g / mol, such as 400,000 to 800,000 g / mol, such as 500,000 to 1,600,000 g / mol, such as 500,000 to 1,200,000 g / mol, such as 500,000 to 1,100,000 g / mol, such as 500,000 to 900,000 g / mol, such as 500,000 to 800,000 g / mol.

[0030] As used herein, unless otherwise stated, the expression z-average molecular weight (Mz) means the z-average molecular weight (Mz) as determined by gel permeation chromatography using a Waters 2695 separation module with a Waters 410 differential refractometer (RI detector), polystyrene standards having molecular weights from about 500 g / mol to 900,000 g / mol, dimethylformamide (DMF) with 0.05 M lithium bromide (LiBr) as the eluent at a flow rate of 0.5 mL / min and an Asahipak GF-510 column for the separation.With respect to polymers having a z-average molecular weight (M2) greater than 900,000 g / mol, the expression z-average molecular weight (Mz) and weight-average molecular weight (Mw) means the z-average molecular weight (Mz) and the weight-average molecular weight (Mw) as determined by gel permeation chromatography (GPC) using a Waters 2695 separation module with a Waters 410 differential refractometer (RI detector), polystyrene standards having molecular weights from about 500 g / mol to 3,000,000 g / mol, dimethylformamide (DMF) with 0.05 M lithium bromide (LiBr) as the eluent at a flow rate of 0.5 mL / min and an Asahipak GF-7M HQ column for the separation.

[0031] The acrylic polymer may comprise a linear polymer forming a linear polymer backbone. Alternatively, the acrylic polymer may comprise a branched polymer comprising several polymer branches. Alternatively, the acrylic polymer may comprise a crosslinked polymer network. The acrylic polymer may also comprise combinations of these polymer geometries, e.g., linear polymers, branched polymers, and / or a crosslinked polymer network.

[0032] The acrylic polymer may be substantially free, essentially free, or completely free of the building blocks comprising the diene monomer residue. As used herein, the acrylic polymer is substantially free of building blocks comprising the diene monomer residue if the building blocks comprising the diene monomer residue are present in the acrylic polymer, if at all, in an amount of less than 2% by weight, based on the total weight of the acrylic polymer. As used herein, the acrylic polymer is essentially free of building blocks comprising the diene monomer residue if the building blocks comprising the diene monomer residue are present in the acrylic polymer, if at all, in an amount of less than 0.1% by weight, based on the total weight of the acrylic polymer.As used herein, the acrylic polymer is completely free of constitutional units comprising the diene monomer residue if the constitutional units comprising the diene monomer residue are not present in the acrylic polymer, i.e., 0% by weight.

[0033] Acrylic polymer may be substantially free, essentially free, or completely free of the constituent units comprising the isobutylene monomer residue. As used herein, acrylic polymer is substantially free of constituent units comprising the isobutylene monomer residue if the constituent units comprising the isobutylene monomer residue are present in the acrylic polymer, if at all, in an amount of less than 2% by weight, based on the total weight of the acrylic polymer. As used herein, acrylic polymer is essentially free of constituent units comprising the isobutylene monomer residue if the constituent units comprising the isobutylene monomer residue are present in the acrylic polymer, if at all, in an amount of less than 0.1% by weight, based on the total weight of the acrylic polymer.As used herein, the acrylic polymer is completely free of constitutional units comprising the isobutylene monomer residue if the constitutional units comprising the isobutylene monomer residue are not present in the acrylic polymer, i.e., 0% by weight. μλ / iyy

[0034] The acrylic polymer may be substantially free, essentially free, or completely free of the residue of monomers comprising three or more ethylenically unsaturated groups per molecule. As used herein, the acrylic polymer is substantially free of constitutional units comprising the residue of monomers comprising three or more ethylenically unsaturated groups per molecule if the constitutional units comprising the residue of monomers comprising three or more ethylenically unsaturated groups per molecule are present in the acrylic polymer, if at all, in an amount of less than 0.1% by weight, based on the total weight of the acrylic polymer.As used herein, the acrylic polymer is essentially free of constitutional units comprising the residue of monomers comprising three or more ethylenically unsaturated groups per molecule if such constitutional units are present in the acrylic polymer, if at all, in an amount of less than 0.01% by weight, based on the total weight of the acrylic polymer. As used herein, the acrylic polymer is completely free of constitutional units comprising the residue of monomers comprising three or more ethylenically unsaturated groups per molecule if such constitutional units are not present in the acrylic polymer, i.e., 0% by weight.

[0035] According to the present invention, the acrylic polymer may be substantially free, essentially free, or completely free of silicon. As used herein, silicon refers to elemental silicon or a silicon-containing compound, such as an organosilicon compound including an alkoxysilane. As used herein, the acrylic polymer is substantially free of silicon if silicon is present in the acrylic polymer in an amount of less than 2% by weight, based on the total weight of the acrylic polymer. As used herein, the acrylic polymer is essentially free of silicon if silicon is present in the acrylic polymer in an amount of less than 1% by weight, based on the total weight of the acrylic polymer. As used herein, the acrylic polymer is completely free of silicon if silicon is not present in the acrylic polymer, i.e., 0% by weight.

[0036] The acrylic polymer can be prepared by polymerizing an ethylenically unsaturated polymerizable monomer composition in a dispersion medium comprising water using 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 may optionally comprise a surfactant to aid in dispersing the monomer composition, and the surfactant may be either a reactive or a non-reactive surfactant. μλ / t / zuzz / uzo ι υ υ Alternatively, the monomer composition can be substantially free, essentially free, or completely free of reactive and / or non-reactive surfactant. The polymerization time and temperature will depend on each other, the selected ingredients, and, in some cases, the scale of the reaction. Polymerization can be carried out, for example, at 40°C to 100°C for 2 to 20 hours.

[0037] The free radical initiator used for polymerization can be selected from any of those used for aqueous latex polymerization techniques, including redox initiators, peroxides, hydroperoxides, peroxydicarbonates, azo compounds, and the like.

[0038] Alternatively, the acrylic polymer can be prepared in an organic solution using techniques well known in the art. For example, the acrylic polymer can be prepared by conventional free-radical initiated solution polymerization techniques, wherein the composition of ethylenically unsaturated monomers is dissolved in a solvent or solvent mixture and polymerized in the presence of a free-radical initiator to form the acrylic polymer comprising the constitutional units comprising the residue of the unsaturated monomers. Examples of suitable solvents that can be used for organic solution polymerization include alcohols, such as ethanol, tertiary butanol, and tertiary amyl alcohol; ketones, such as acetone and methyl ethyl ketone; and ethers, such as ethylene glycol dimethyl ether.Examples of suitable free radical initiators include those soluble in the monomer mixture, such as azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), azobis(α,γ-dimethylvaleronitrile), tertiary butyl perbenzoate, tertiary butyl peracetate, benzoyl peroxide, and ditertiary butyl peroxide. The free radical initiator can be present in an amount of 0.01% to 6% by weight, such as 1.0% to 4.0% by weight, or 2.0% to 3.5% by weight, depending on the total weight of the acrylic polymer. In these examples, the solvent should first be heated to reflux, and a mixture of the ethylenically unsaturated monomer composition and a free radical initiator can then be slowly added to the refluxing solvent. The reaction mixture can be maintained at polymerization temperatures to reduce the free monomer content below 1.0%, such as below 0.5% by weight, based on the total weight of the ethylenically unsaturated monomer composition. The polymerization time and temperature may depend on each other, the selected ingredients, and, in some cases, the scale of the reaction. For example, polymerization can be carried out at 40°C to 100°C for 2 to 20 hours.

[0039] Ionic groups in the acrylic polymer, if present, can be formed by at least partially neutralizing basic or acidic groups present in the acrylic polymer with an acid or base, respectively. The charge of the ionic groups in the polymer can be neutralized by counterions. The ionic groups and charge-neutralizing counterions can together form salt groups, so that the acrylic polymer can comprise an acrylic polymer containing an ionic salt group.

[0040] Accordingly, the acrylic polymer, prior to or during dispersion in a dispersion medium comprising water, may be at least partially neutralized, for example, by treatment with an acid to form an acrylic polymer containing a water-dispersible cationic salt group. As used herein, the term "acrylic polymer containing a cationic salt group" refers to a cationic acrylic polymer comprising at least partially neutralized cationic functional groups, such as sulfonium and ammonium groups, which impart a positive charge. Non-limiting examples of suitable acids include inorganic acids such as phosphoric acid and sulfamic acid, as well as organic acids such as acetic acid and lactic acid, among others.In addition to acids, salts such as dimethylhydroxyethylammonium dihydrogen phosphate and ammonium dihydrogen phosphate can be used to at least partially neutralize the acrylic polymer. The acrylic polymer can be neutralized to at least 50%, such as at least 70%, or at least 100% or more of the total theoretical neutralization equivalent. As used herein, the total theoretical neutralization equivalent refers to a percentage of the stoichiometric amount of acid relative to the total amount of basic groups, such as amino groups, theoretically present in the polymer. Besides using amino groups containing ethionically unsaturated monomers, amino groups can also be optionally incorporated into the cationic acrylic polymer by reacting an amine with epoxide functional groups present in the acrylic polymer (if present).The dispersion step can be achieved by combining the acrylic polymer, which contains a neutralized or partially neutralized cationic salt group, with the dispersion medium of the dispersion phase. Neutralization and dispersion can also occur simultaneously in a single step by combining the acrylic polymer and the dispersion medium. The acrylic polymer (or its salt) can be added to the dispersion medium, or vice versa. Monomers can also be neutralized prior to polymerization to form the acrylic polymer. The pH of the dispersion can range from 3 to 9.

[0041] According to the present invention, the acrylic polymer can be at least partially neutralized, before or during dispersion in a dispersion medium comprising water, for example, by treatment with a base to form an acrylic polymer containing a water-dispersible anionic salt group. As used herein, the term "acrylic polymer containing an anionic salt group" refers to an anionic acrylic polymer comprising at least partially neutralized anionic functional groups, such as carboxylic acid and phosphoric acid groups that impart a negative charge. Non-limiting examples of suitable bases are amines, such as, for example, tertiary amines. Specific examples of suitable amines include, but are not limited to, trialkylamines and dialkylalkoxyamines, such as triethylamine, diethylethanolamine, and dimethylethanolamine.The acrylic polymer can be neutralized to at least 50%, or at least 70%, or at least 100% or more, of the total theoretical neutralization equivalent. The dispersion step can be achieved by combining the acrylic polymer containing a neutralized or partially neutralized anionic salt group with the dispersion medium of the dispersion phase. Neutralization and dispersion can also occur simultaneously in a single step by combining the acrylic polymer and the dispersion medium. The acrylic polymer (or its salt) can be added to the dispersion medium, or the dispersion medium can be added to the acrylic polymer (or its salt). The pH of the dispersion can be within the range of 3 to 9.

[0042] The free radical initiator used for the polymerization of the acrylic polymer can be selected from any of those used for aqueous acrylic polymerization techniques, including redox initiators, peroxides, hydroperoxides, peroxydicarbonates, azo compounds, and the like.

[0043] In aqueous latex polymerization or solution polymerization techniques, the free radical initiator may be present in an amount of 0.01% to 7% by weight, such as 0.05% to 2.0% by weight, or 0.1% to 1.5% by weight, depending on the acrylic polymer monomer composition. A chain transfer agent that is soluble in the monomer composition, such as alkyl mercaptans, for example, tertiary dodecyl mercaptan, 2-mercaptoethanol, isooctyl mercaptopropionate, noctyl mercaptan, or 3-mercapto acetic acid, may be used in the acrylic polymer polymerization. Other chain transfer agents such as ketones, for example, methyl ethyl ketone, and chlorocarbons such as chloroform, may also be used. The amount of chain transfer agent, if present, can be from 0.1% to 6.0% by weight, depending on the weight of the acrylic polymer.Multifunctional mercaptans with relatively high molecular weights can be substituted, in whole or in part, for the chain transfer agent. For example, these molecules can range in molecular weight from approximately 94 to 1,000 g / mol or more. Their functionality can range from approximately 2 to approximately 4. The amounts of these multifunctional mercaptans, if present, can range from 0.1% to 6.0% by weight, depending on the weight of the acrylic polymer monomer composition.

[0044] According to the present invention, water may be present in the aqueous dispersion of the acrylic polymer in amounts from 40% to 99% by weight, such as from 50% to 75% by weight, depending on the total weight of the aqueous dispersion. The acrylic polymer may be added to the other components of the electrodepositable coating composition as an aqueous dispersion of the acrylic polymer.

[0045] In addition to water, the dispersion medium may also comprise organic cosolvents. Organic cosolvents may be at least partially soluble in water. Examples of such solvents include oxygenated organic solvents, such as monoalkyl ethers of ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol containing 1 to 10 carbon atoms in the alkyl group, such as the monoethyl and monobutyl ethers of these glycols. Examples of other solvents at least partially miscible in water include alcohols such as ethanol, isopropanol, butanol, and diacetone. If used, the organic cosolvents may be present in an amount less than 10% by weight, such as less than 5% by weight, based on the total weight of the dispersion medium.

[0046] The acrylic polymer of the present invention may be a single-stage acrylic polymer. As used herein, the term single-stage acrylic polymer refers to a polymer produced in a single stage of polymerization of unsaturated monomers and not through multi-stage polymerization where a first polymer is formed and then additional monomer stages are further polymerized with the first polymer.

[0047] The acrylic polymer described above may be present in the electrodepositable coating composition in an amount of at least 0.05 wt%, such as at least 0.1 wt%, such as at least 0.2 wt%, such as at least 0.4 wt%, such as at least 0.5 wt%, such as at least 1 wt%, based on the total weight of resin solids in the electrodepositable coating composition. The acrylic polymer may be present in the electrodepositable coating composition in an amount not greater than 10 wt%, such as not greater than 3 wt%, such as not greater than 2 wt%, such as not greater than 1 wt%, such as not greater than 0.85 wt%, based on the total weight of resin solids in the electrodepositable coating composition. The acrylic polymer may be present in the electrodepositable coating composition in an amount of 0.05% to 10% by weight, such as 0.1% to 10% by weight, such as 0.2% to 10% by weight, such as 0.4% to 10% by weight, such as 0.5% to 10% by weight, such as 1% to 10% by weight, such as 0.05% to 3% by weight, such as 0.1% to 3% by weight, such as 0.2% to 3% by weight, such as 0.4% to 3% by weight, such as 0.5% to 3% by weight, such as 1% to 3% by weight, such as 0.05% to 2% by weight, such as 0.1% to 2% by weight, such as 0.2% to 2% by weight, such as 0.4% to 2% by weight, such as 0.5% to 2% by weight, such as 1% to 2% by weight, such as 0.5% to 1% by weight, as 0.1% to 1% in weight, such as 0.2% to 1% by weight, such as 0.4% to 1% by weight, 0.5% to 1% by weight, such as 0.05% to 0.85% by weight, such as 0.1% to 0.85% by weight, 0.2% to 0.85% by weight, such as 0.4% to 0.85% by weight, such as 0.5% to 0.85% by weight, based on the total weight of resin solids in the electrodepositable coating composition.

[0048] It has been surprisingly discovered that the use of the acrylic polymer in an electrodepositable coating composition in the amounts taught herein results in a deposited coating that has improved edge coverage and crater resistance. In addition, it has been surprisingly discovered that the use of the acrylic polymer in an electrodepositable coating composition results in deposited coatings that have low gloss.

[0049] The presence of the acrylic polymer in the amounts disclosed herein in an electrodepositable coating composition may result in a reduction in the depth of craters formed in the cured coating during the curing of the electrodepositable coating composition compared to a substrate coated with a comparative electrodepositable coating composition that does not include the acrylic polymer but otherwise has the same composition as the electrodepositable coating composition.

[0050] The presence of the acrylic polymer in the amounts disclosed herein in an electrodepositable coating composition may result in an increase in the average edge coverage percentage of the resulting cured coating. For example, the average edge coverage percentage may be improved by at least 20%, such as at least 40%, such as at least 60%, as measured in accordance with the drill edge coverage test method described in the Examples section below, compared to a substrate coated with a comparator electrodepositable coating composition that does not include the acrylic polymer but is otherwise of the same composition as the electrodepositable coating composition.

[0051] The presence of acrylic polymer in the amounts disclosed herein in an electrodepositable coating composition may result in a reduction of the gloss of the cured coating. For example, coating compositions having acrylic polymer present in an amount of 0.5 wt%, based on total resin solids, may result in a cured coating having a 20° reduction in gloss value of at least 20%, such as at least 40%, such as at least 50%, such as at least 60%, compared to a comparable electrodepositable coating composition that does not include acrylic polymer but has the same composition. For example, coating compositions having acrylic polymer present in an amount of 0.A 5% by weight, based on total resin solids, can result in a cured coating that has a 60° gloss reduction of at least 10%, such as at least 20%, such as at least 25%, such as at least 30%, such as at least 40%, compared to a comparable electrodepositable coating composition that does not include the acrylic polymer but is otherwise of the same composition. The gloss values ​​of the cured coating can be measured (µl / t / zuzz / uzo i yy) with a BYK Gardner turbidity meter (catalog No. 4601) in accordance with ASTM D523. It should be noted that the acrylic polymer of the present invention can result in the low gloss property with less acrylic polymer present in the coating composition than other low gloss additives known in the art.As used herein, gloss reduction refers to the percentage decrease in the gloss value of a cured coating compared to a comparator coating and is determined by dividing the gloss value of the experimental coating by the gloss value of the comparator coating and multiplying by 100, where the comparator coating is the result of a comparative coating composition that is the same as the experimental coating composition with the exception of the acrylic polymer. The degree of gloss reduction will depend on a number of factors, including the gloss of the comparator coating.For example, a person of mid-level trade would expect the addition of acrylic polymer to a coating composition that already produces a coating that has a relatively low gloss to result in a lower reduction in the % gloss value with the addition of the acrylic polymer than an addition to a coating composition that produces a coating that has a relatively high gloss. Film-forming polymer containing an ionic salt group

[0052] According to the present invention, the electrodepositable coating composition may further comprise a film-forming polymer containing an ionic salt group. The film-forming polymer containing an ionic salt group is different from the acrylic polymer described above.

[0053] According to the present invention, the film-forming polymer containing an ionic salt group may comprise a film-forming polymer containing a cationic salt group. The film-forming polymer containing a cationic salt group may be used in a cationic electrodepositable coating composition. As used herein, the expression "film-forming polymer containing a cationic salt group" refers to polymers that include at least partially neutralized cationic groups, such as sulfonium and ammonium groups, which impart a positive charge. As used herein, the term "polymer" encompasses, among others, oligomers and both homopolymers and copolymers. The film-forming polymer containing a cationic salt group may comprise active hydrogen functional groups.As used herein, the term "active hydrogen functional groups" refers to those groups that are reactive with isocyanates as determined by the Zerewitinoff test described above and includes, for example, hydroxyl groups, primary or secondary amine groups, and thiol groups. Film-forming polymers that contain a cationic salt group comprising active hydrogen functional groups may be termed film-forming polymers containing a cationic salt group containing active hydrogen.

[0054] Examples of polymers that are suitable for use as the film-forming polymer containing a cationic salt group in the present invention include, among others, alkyd polymers, acrylics, polyepoxides, polyamides, polyurethanes, polyureas, polyethers, and polyesters.

[0055] More specific examples of film-forming polymers containing an active hydrogen-containing cationic salt group include polyepoxiamine adducts, such as the adduct of a polyglycidyl ether of a polyphenol, such as bisphenol A, and primary and / or secondary amines, such as those described in U.S. Patent No. 4,031,050 from column 3, line 27 to column 5, line 50; U.S. Patent No. 4,452,963 from column 5, line 58 to column 6, line 66; and U.S. Patent No. 6,017,432 from column 2, line 66 to column 6, line 26, portions of which are incorporated herein by reference. A portion of the amine that is reacted with the polyepoxide can be a cetimine of a polyamine, as described in U.S. Patent No. 4,104,147 from column 6, line 23 to column 7, line 23, the cited portion of which is incorporated herein by reference.Also suitable are non-gelled polyepoxide-polyoxyalkylenepolyamine resins, such as those described in U.S. Patent No. 4,432,850 from column 2, line 60 to column 5, line 58, the cited portion of which is incorporated herein by reference. In addition, cationic acrylic resins, such as those described in U.S. Patent No. 3,455,806 from column 2, line 18 to column 3, line 61; and 3,928,157 from column 2, line 29 to column 3, line 21, portions of which are incorporated herein by reference, may be used.

[0056] In addition to resins containing an amine salt group, resins containing a quaternary ammonium salt group can also be used as a film-forming polymer containing a cationic salt group in the present invention. Examples of such resins are those formed from the reaction of an organic polyepoxide with a tertiary amine acid salt. Such resins are described in U.S. Patent Nos. 3,962,165 from column 2, line 3 to column 11, line 7; 3,975,346 from column 1, line 62 to column 17, line 25; and 4,001,156 from column 1, line 37 to column 16, line 7, portions of which are incorporated herein by reference. Examples of other suitable cationic resins include resins containing a ternary sulfonium salt group, such as those described in U.S. Patent No.3,793,278 from column 1, line 32 to column 5, line 20, part of which is incorporated herein by reference. In addition, cationic resins cured by a transesterification mechanism, such as those described in European patent application No. 12463B1 on page 2, line 1 to page 6, line 25, part of which is incorporated herein by reference, may also be used. [OO57]Other suitable film-forming polymers containing a cationic salt group include those capable of forming photodegradation-resistant electrodepositable coating compositions. Such polymers include polymers comprising cationic amine salt groups derived from dangling and / or amino-terminus groups disclosed in U.S. Patent Application Publication No. 2003 / 0054193 A1 from paragraph

[0064] to paragraph

[0088] , a portion of which is incorporated herein by reference. Also suitable are resins containing a cationic salt group containing active hydrogen derived from a polyglycidyl ether of a polyhydric phenol that is essentially free of aliphatic carbon atoms to which more than one aromatic group is attached, as described in U.S. Patent Application Publication No.° 2003 / 0054193 From paragraph

[0096] to paragraph

[0123] , part which is incorporated herein by reference.

[0058] The film-forming polymer containing an active hydrogen-containing cationic salt group is made cationic and water-dispersible by at least partial neutralization with an acid. Suitable acids include organic 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. Sulfamic acid means sulfamic acid itself or derivatives thereof, such as those having the formula: RI H— N— SO H where R is hydrogen or an alkyl group having 1 to 4 carbon atoms. Mixtures of the acids mentioned above may also be used in the present invention.

[0059] The extent of neutralization of a film-forming polymer containing a cationic salt group may vary with the particular polymer involved. However, sufficient acid must be used to adequately neutralize the film-forming polymer containing a cationic salt group so that it can be dispersed in an aqueous dispersion medium. For example, the amount of acid used may provide at least 20% of the total theoretical neutralization. Excess acid beyond the amount required for 100% total theoretical neutralization may also be used. For example, the amount of acid used to neutralize the film-forming polymer containing a cationic salt group may be 10.1%, depending on the total amines in the film-forming polymer containing an active hydrogen salt group.Alternatively, the amount of acid used to neutralize the film-forming polymer containing a cationic salt group with active hydrogen can be 1100%, depending on the total amines in the film-forming polymer. The total amount of acid used to neutralize the film-forming polymer can vary among any combination of values, which are indicated in the preceding sentences and include the stated values. For example, the total amount of acid used to neutralize the film-forming polymer containing a cationic salt group with active hydrogen can be 20%, 35%, 50%, 60%, or 80%, depending on the total amines in the film-forming polymer.

[0060] According to the present invention, the film-forming polymer containing a cationic salt group may be present in the cationic electrodepositable coating composition in an amount of at least 40% by weight, such as at least 50% by weight, such as at least 60% by weight, and may be present in an amount not greater than 90% by weight, such as not greater than 80% by weight, such as not greater than 75% by weight, depending on the total weight of the resin solids in the electrodepositable coating composition. The film-forming polymer containing a cationic salt group may be present in the cationic electrodepositable coating composition in an amount of 40% to 90% by weight, such as 50% to 80% by weight, such as 60% to 75% by weight, depending on the total weight of the resin solids in the electrodepositable coating composition.As used herein, the resin solids include the film-forming polymer containing an ionic salt group, the curing agent, the acrylic polymer, and any additional water-dispersible non-pigmented components present in the electrodepositable coating composition.

[0061] According to the present invention, the film-forming polymer containing an ionic salt group may comprise a film-forming polymer containing an anionic salt group. As used herein, the expression "film-forming polymer containing an anionic salt group" refers to an anionic polymer comprising at least partially neutralized anionic functional groups, such as carboxylic acid and phosphoric acid groups that impart a negative charge. As used herein, the term "polymer" encompasses, among others, oligomers and both homopolymers and copolymers. The film-forming polymer containing an anionic salt group may comprise active hydrogen functional groups.As used herein, the term "active hydrogen functional groups" refers to those groups that are reactive with isocyanates as determined by the Zerewitinoff test described above and includes, for example, hydroxyl groups, primary or secondary amine groups, and thiol groups. Film-forming polymers containing an anionic salt group comprising active hydrogen functional groups may be referred to as film-forming polymers containing an anionic salt group containing active hydrogen. The film-forming polymer containing an anionic salt group may be used in an anionic electrodepositable coating composition.

[0062] The film-forming polymer containing an anionic salt group may comprise base-solubilized film-forming polymers containing a carboxylic acid group, such as the reaction product or adduct of a drying oil or semi-drying fatty acid ester with a dicarboxylic acid or anhydride; and the reaction product of a fatty acid ester, unsaturated acid, or anhydride and any additional unsaturated modifying material further reacted with polyol. Also suitable are at least partially neutralized interpolymers of hydroxyalkyl esters of unsaturated carboxylic acids, unsaturated carboxylic acid, and at least one other ethylenically unsaturated monomer. Yet another suitable anionic electrodepositable resin comprises an alkydaminoplast vehicle, i.e., a vehicle containing an alkyd resin and an aminealdehyde resin.Another suitable anionic electrodepositable resin composition comprises mixed esters of a resinous polyol. Other acidic functional polymers, such as phosphated polyepoxide or phosphated acrylic polymers, may also be used. Example phosphated polyepoxides are disclosed in U.S. Patent Application Publication No. 2009-0045071 at

[0004]

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

[0014] -

[0040] , the cited portions of which are incorporated herein by reference. Resins comprising one or more pendant carbamate functional groups, such as those described in U.S. Patent No. 6,165,338, are also suitable.

[0063] According to the present invention, the film-forming polymer containing an anionic salt group may be present in the anionic electrodepositable coating composition in an amount of at least 50% by weight, such as at least 55% by weight, such as at least 60% by weight, and may be present in an amount not greater than 90% by weight, such as not greater than 80% by weight, such as not greater than 75% by weight, depending on the total weight of the resin solids of the electrodepositable coating composition. The film-forming polymer containing an anionic salt group may be present in the anionic electrodepositable coating composition in an amount of 50% to 90%, such as 55% to 80%, such as 60% to 75%, depending on the total weight of the resin solids of the electrodepositable coating composition.As used herein, the resin solids include the film-forming polymer containing an ionic salt group, the curing agent, the acrylic polymer, and any additional water-dispersible non-pigmented components present in the electrodepositable coating composition. Curing agent

[0064] According to the present invention, the electrodepositable coating composition of the present invention may further comprise a curing agent. The curing agent may be reactive with the acrylic polymer and the film-forming polymer containing an ionic salt group. The curing agent may react with reactive groups, such as active hydrogen groups, of the film-forming polymer containing an ionic salt group and the acrylic polymer to cure the coating composition to form a coating. As used herein, the term "cure," "cured," or the like, as used in connection with the electrodepositable coating compositions described herein, means that at least a portion of the components forming the electrodepositable coating composition crosslinks to form a coating.Furthermore, the curing of an electrodepositable coating composition refers to subjecting that composition to curing conditions (e.g., elevated temperature) that lead to the reaction of the reactive functional groups of the components of the electrodepositable coating composition, resulting in crosslinking of the components and the formation of a coating that is at least partially cured. Non-limiting examples of curing agents include at least partially blocked polyisocyanates, aminoplast resins, and phenolplast resins, such as phenol-formaldehyde condensates, including allyl ether derivatives thereof.

[0065] Suitable at least partially blocked polyisocyanates include aliphatic polyisocyanates, aromatic polyisocyanates, and mixtures thereof. The curing agent may comprise an at least partially blocked aliphatic polyisocyanate. Suitable at least partially blocked aliphatic polyisocyanates include, for example, completely blocked aliphatic polyisocyanates, such as those described in U.S. Patent No. 3,984,299 from column 1, line 57 to column 3, line 15, a portion of which is incorporated herein by reference, or partially blocked aliphatic polyisocyanates reacting with the polymer backbone, as described in U.S. Patent No. 3,947,338 from column 2, line 65 to column 4, line 30, a portion of which is also incorporated herein by reference.Blocked means that the isocyanate groups were reacted with a compound in such a way that the resulting blocked isocyanate group is stable to activate hydrogens at room temperature, but reactive with active hydrogens in the film-forming polymer at elevated temperatures, such as between 90°C and 200°C. The polyisocyanate curing agent may be a completely blocked polyisocyanate with substantially no free isocyanate groups.

[0066] The polyisocyanate curing agent may comprise a diisocyanate, higher functional polyisocyanates, or combinations thereof. For example, the polyisocyanate curing agent may comprise aliphatic and / or aromatic polyisocyanates.Aliphatic polyisocyanates may include (i) alkylene isocyanates, such as trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, ethylidene diisocyanate, and butylidene diisocyanate, and (ii) cycloalkylene isocyanates, such as 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,2-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate) (HMDI), the cyclotrimer of 1,6-hexmethylene diisocyanate (also known as the HDI isocyanurate trimer (commercially available as Desmodur N3300 through Convestro AG) and metatetramethylxylylene diisocyanate (commercially available as TMXDI® through Allnex SA).Aromatic polyisocyanates may include (i) arylene isocyanates, such as m-phenylene diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate and 1,4-naphthalene diisocyanate and (ii) alkarylene isocyanates, such as 4,4'-diphenylene methane (MDI), 2,4-tolylene diisocyanate or 2,6-tolylene diisocyanate (TDI), or mixtures thereof, 4,4-toluidine diisocyanate and xylylene diisocyanate. Triisocyanates, such as triphenylmethan-4,4',4-triisocyanate, benzene 1,3,5-triisocyanate, and toluene 2,4,6-triisocyanate, tetraisocyanates, such as 4,4'-diphenyldimethylmethan n-2,2',5,5'-tetraisocyanate, and polymerized polyisocyanates, such as tolylene diisocyanate dimers and trimers, may also be used. The curing agent may comprise a polyisocyanate blocked from a polymeric polyisocyanate, such as polymeric HDI, polymeric MDI, polymeric isophorone diisocyanate, and the like.The curing agent may also comprise a blocked trimer of hexamethylene diisocyanate available as Desmodur N3300® through Covestro AG. Mixtures of polyisocyanate curing agents may also be used.

[0067] The polyisocyanate curing agent may be at least partially blocked with at least one blocking agent selected from a 1,2-alkanediol, for example, 1,2-propanediol; a 1,3-alkanediol, for example, 1,3-butanediol; a benzyl alcohol, for example, benzyl alcohol; an allylic alcohol, for example, allyl alcohol; caprolactam; a dialkylamine, for example, dibutylamine; and mixtures thereof. The polyisocyanate curing agent may be at least partially blocked with at least one 1,2-alkanediol having three or more carbon atoms, for example, 1,2-butanediol. [OO68]Other suitable blocking agents include aliphatic, cycloaliphatic, or aromatic alkyl monoalcohols or phenolic compounds, including, for example, lower aliphatic alcohols such as methanol, ethanol, and n-butanol; cycloaliphatic alcohols such as cyclohexanol; aromatic alkyl alcohols such as phenyl carbinol and methylphenyl carbinol; and phenolic compounds such as phenol itself and substituted phenols, where the substituents do not affect the coating operations, such as cresol and nitrophenol. Glycol ethers and glycol amines can also be used as blocking agents. Glycol ethers include ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether, and propylene glycol methyl ether. Other suitable blocking agents include oximes, such as methyl ethyl ketoxime, acetone oxime, and cyclohexanone oxime.

[0069] The curing agent may comprise an aminoplast resin. Aminoplast resins are condensation products of an aldehyde with a substance having an amino or amide group. Condensation products obtained from the reaction of alcohols and an aldehyde with melamine, urea, or benzoguanamine may be used. However, condensation products of other amines and amides may also be used, for example, aldehyde condensates of triazines, diazines, triazoles, guanidines, guanamines, and alkyl- and aryl-substituted derivatives of such compounds, including alkyl- and aryl-substituted ureas and alkyl- and aryl-substituted melamines. Some examples of such compounds are N,N'-dimethyl urea, benzourea, dicyandiamide, formaguanamine, acetoguanamine, amelin, 2-chloro-4,6-diamino-l,3,5-trazine, 6-methyl-2,4-diamino-l,3,5-trazine, 3,5-diaminotriazole, triaminopyrimidine, 2-mercapto-4,6-diaminopyrimidine, 3,4,6-tris(ethylamine)-l,3,5-trazine and the like.Aldehydes include formaldehyde, acetaldehyde, crotonaldehyde, acrolein, benzaldehyde, furfural, glyoxal, and similar compounds.

[0070] Aminoplast resins may contain methylol or similar alkylol groups, and at least a portion of these alkylol groups may be etherified by reaction with an alcohol to provide solvent-soluble organic resins. Any monohydric alcohol may be used for this purpose, including alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, and others, as well as benzyl alcohol and other aromatic alcohols, cyclic alcohols such as cyclohexanol, glycol monoethers such as CELLOSOLVE and CARBITOL, and alcohols substituted with halogens and other substituents, such as 3-chloropropanol and butoxyethanol.

[0071] Non-limiting examples of commercially available aminoplast resins include those available under the trade names CYMEL® through Allnex Belgium SA / NV, such as CYMEL 1130 and 1156, and RESIMENE® through INEOS Melamines, such as RESIMENE 750 and 753. Examples of suitable aminoplast resins include those described in U.S. Patent No. 3,937,679 from column 16, line 3, through column 17, line 47, a portion of which is incorporated herein by reference. As disclosed in the aforementioned portion of patent '679, aminoplast can be used in combination with methyl phenol ethers.

[0072] Phenoplast resins are formed by the condensation of an aldehyde and a phenol. Suitable aldehydes include formaldehyde and acetaldehyde. Methylene-releasing and aldehyde-releasing agents, such as paraformaldehyde and hexamethylene tetramine, can also be used as the aldehyde agent. Various phenols can be used, such as phenol itself, a cresol, or a phenol substituted with a hydrocarbon radical having a linear or branched chain, or a cyclic structure substituted with hydrogen on the aromatic ring. Mixtures of phenols can also be used. Some specific examples of suitable phenols are p-phenylphenol, p-tert-butylphenol, p-tert-amylphenol, cyclopentylphenol, and phenols substituted with unsaturated hydrocarbon, such as monobutenylphenols containing a butenyl group in the ortho, meta, or para position, and where the double bond occurs at various positions in the hydrocarbon chain.

[0073] Aminoplast and phenoplast resins, as described above, are described in U.S. Patent No. 4,812,215 from column 1.6, line 20, to column 7, line 12, the quoted portion of which is incorporated herein by reference.

[0074] The curing agent may be present in the cationic electrodepositable coating composition in an amount of at least 10% by weight, such as at least 20% by weight, such as at least 25% by weight, and may be present in an amount not greater than 60% by weight, such as not greater than 59.95% by weight, such as not greater than 50% by weight, such as not greater than 40% by weight, depending on the total weight of the resin solids in the electrodepositable coating composition. The curing agent may be present in the cationic electrodepositable coating composition in an amount of 10% to 60% by weight, such as 10% to 59.95% by weight, such as 20% to 50% by weight, such as 25% to 40% by weight, depending on the total weight of the resin solids in the electrodepositable coating composition.

[0075] The curing agent may be present in the anionic electrodepositable coating composition in an amount of at least 10% by weight, such as at least 20% by weight, such as at least 25% by weight, and may be present in an amount not greater than 50% by weight, such as not greater than 45% by weight, such as not greater than 40% by weight, depending on the total weight of the resin solids in the electrodepositable coating composition. The curing agent may be present in the anionic electrodepositable coating composition in an amount of 10% to 50% by weight, such as 20% to 45% by weight, such as 25% to 40% by weight, depending on the total weight of the resin solids in the electrodepositable coating composition. ma / iyy Additional components of electrodepositable coating compositions

[0076] The electrodepositable coating composition according to the present invention may optionally comprise one or more other components in addition to the acrylic polymer, the film-forming polymer containing an ionic salt group, and the curing agent described above.

[0077] According to the present invention, the electrodepositable coating composition may optionally comprise a catalyst for catalyzing the reaction between the curing agent and the polymers. Examples of suitable catalysts for cationic electrodepositable coating compositions include, but are not limited to, organotin compounds (e.g., dibutyltin oxide and dioctyltin oxide) and salts thereof (e.g., dibutyltin diacetate); other metal oxides (e.g., cerium, zirconium, and bismuth oxides) and salts thereof (e.g., bismuth sulfamate and bismuth lactate); or a cyclic guanidine as described in U.S. Patent No. 7,842,762 from 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.Examples of suitable catalysts for anionic electrodepositable coating compositions include latent acid catalysts, specific examples of which are identified in WO 2007 / 118024 at

[0031] and include, but are not limited to, ammonium hexafluoroantimonate, quaternary salts of SbFs (e.g., NACURE® XC7231), t-amine salts of SbFe (e.g., NACURE® XC-9223), Zn salts of triflic acid (e.g., NACURE® A202 and A218), quaternary salts of triflic acid (e.g., NACURE® XCA230), and diethylamine salts of triflic acid (e.g., NACURE® A233), all commercially available through King Industries, and / or mixtures thereof. Latent acid catalysts can be formed by preparing a derivative of an acid catalyst, such as para-toluenesulfonic acid (pTSA) or other sulfonic acids.For example, a well-known group of blocked acid catalysts are amine salts of aromatic sulfonic acids, such as pyridinium para-toluenesulfonate. Such sulfonate salts are less active than the free acid in promoting crosslinking. During curing, the catalysts can be activated by heat.

[0078] According to the present invention, the electrodepositable coating compositions of the present invention may optionally comprise crater control additives that can be incorporated into the coating composition, such as, for example, a polyalkylene oxide polymer that may comprise a copolymer of butylene oxide and propylene oxide. According to the present invention, the molar ratio of butylene oxide to propylene oxide may be at least 1:1, such as at least 3:1, such as at least 5:1, and in some cases, may be no greater than 50:1, such as no greater than 30:1, such as no greater than 20:1. According to the present invention, the molar ratio of butylene oxide to propylene oxide can be from 1:1 to 50:1, such as from 3:1 to 30:1, such as from 5:1 to 20:1.

[0079] The polyalkylene oxide polymer may comprise at least two functional hydroxyl groups and may be monofunctional, difunctional, trifunctional, or tetrafunctional. As used herein, a functional hydroxyl group comprises one -OH group. For clarity, the polyalkylene oxide polymer may comprise additional functional groups in addition to the functional hydroxyl groups. As used herein, monofunctional, when used with respect to the number of functional hydroxyl groups comprising a particular monomer or polymer, means a monomer or polymer comprising one (1) functional hydroxyl group per molecule. As used herein, difunctional, when used with respect to the number of functional hydroxyl groups comprising a particular monomer or polymer, means a monomer or polymer comprising two (2) functional hydroxyl groups per molecule.As used herein, trifunctional, when used with respect to the number of functional hydroxyl groups comprising a particular monomer or polymer, means a monomer or polymer comprising three (3) functional hydroxyl groups per molecule. As used herein, tetrafunctional, when used with respect to the number of functional hydroxyl groups comprising a particular monomer or polymer, means a monomer or polymer comprising four (4) functional hydroxyl groups per molecule.

[0080] The hydroxyl equivalent weight of the polyalkylene oxide polymer may be at least 100 g / mol, such as at least 200 g / mol, such as at least 400 g / mol, and may not be greater than 2,000 g / mol, such as not greater than 1,000 g / mol, such as not greater than 800 g / mol. The hydroxyl equivalent weight of the polyalkylene oxide polymer may be from 100 g / mol to 2,000 g / mol, such as from 200 g / mol to 1,000 g / mol, such as from 400 g / mol to 800 g / mol. As used herein, with respect to the polyalkylene oxide polymer, the hydroxyl equivalent weight is determined by dividing the molecular weight of the polyalkylene oxide polymer by the number of hydroxyl groups present in the polyalkylene oxide polymer.

[0081] The polyalkylene oxide polymer may have an average molecular weight at z (Mz) of at least 200 g / mol, such as at least 400 g / mol, such as at least 600 g / mol, and may be no greater than 5,000 g / mol, such as no greater than 3,000 g / mol, such as no greater than 2,000 g / mol. According to the present invention, the polyalkylene oxide polymer may have an average molecular weight at z (Mz) of 200 g / mol to 5,000 g / mol, such as from 400 g / mol to 3,000 g / mol, such as from 600 g / mol to 2,000 g / mol.As used herein, with respect to polyalkylene oxide polymers having an average molecular weight at z (Mz) of less than 900,000, the expression average molecular weight at z (Mz) means that the average molecular weight ma / t / zuzz / uzo ι yy at z (Mz) as determined by gel permeation chromatography using a Waters 2695 separation module with a Waters 410 differential refractometer (RI detector), polystyrene standards having molecular weights from about 500 g / mol to 900,000 g / mol, tetrahydrofuran (THF) with 0.05 M lithium bromide (LiBr) as the eluent at a flow rate of 0.5 mL / min and an Asahipak GF-510 column for the separation.

[0082] The polyalkylene oxide polymer may be present in the electrodepositable coating composition in an amount of at least 0.1% by weight based on the total weight of the resin mixture solids, such as at least 0.5% by weight, such as at least 0.75% by weight, and in some instances, it may be present in the electrodepositable coating composition in an amount not greater than 10% by weight based on the total weight of the resin mixture solids, such as not greater than 4% by weight, such as not greater than 3% by weight. The polyalkylene oxide polymer may be present in the electrodepositable coating composition in an amount from 0.1% to 10% by weight based on the total weight of the resin mixture solids, such as from 0.5% to 4% by weight, such as from 0.75% to 3% by weight.

[0083] According to the present invention, the electrodepositable coating composition may comprise other optional ingredients, such as a pigment composition and, if desired, various additives such as fillers, plasticizers, antioxidants, biocides, UV light absorbers and stabilizers, hindered amine light stabilizers, foam removers, fungicides, dispersion aids, flow control agents, surfactants, wetting agents, or combinations thereof. Alternatively, the electrodepositable coating composition may be completely free of any of the optional ingredients, i.e., the optional ingredient is not present in the electrodepositable coating composition.The pigment composition may include, for example, iron oxides, lead oxides, strontium chromate, carbon black, carbon powder, titanium dioxide, talc, barium sulfate, as well as color pigments such as cadmium yellow, cadmium red, chromium yellow, and the like. The pigment content of the dispersion can be expressed as the weight ratio of pigment to resin and may range from 0.03 to 0.6 when pigment is used. The other additives mentioned above may be present in the electrodepositable coating composition in amounts from 0.01% to 3% by weight, depending on the total weight of resin solids in the electrodepositable coating composition.

[0084] According to the present invention, the electrodepositable coating composition may comprise water and / or one or more organic solvents. For example, water may be present in amounts of 40% to 90% by weight, such as 50% to 75% by weight, depending on the total weight of the electrodepositable coating composition. Examples of suitable organic solvents include oxygenated organic solvents, such as monoalkyl ethers of ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol containing 1 to 10 carbon atoms in the alkyl group, such as the monoethyl and monobutyl ethers of these glycols. Examples of other solvents at least partially miscible in water include alcohols such as ethanol, isopropanol, butanol, and diacetone.If used, organic solvents may generally be present in amounts less than 10% by weight, such as less than 5% by weight, depending on the total weight of the electrodepositable coating composition. The electrodepositable coating composition may be provided, in particular, in the form of a dispersion, such as an aqueous dispersion.

[0085] According to the present invention, 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 not exceed 50% by weight, such as not exceeding 40% by weight, or not exceeding 20% ​​by weight, depending 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, or from 5% to 20% by weight, depending 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. Substrates

[0086] According to the present invention, the electrodepositable coating composition can be electrophoretically applied to a substrate. The electrodepositable coating composition can be electrophoretically deposited onto any electrically conductive substrate. Suitable substrates include metal substrates, metal alloy substrates, and / or metallized substrates, such as nickel-plated plastic. Additionally, the substrates may comprise non-metallic conductive materials, including composite materials such as, for example, materials comprising carbon fibers or conductive carbon.According to the present invention, the metal or metal alloy may comprise, for example, cold-rolled steel, hot-rolled steel, zinc-coated steel, zinc compounds, or zinc alloys, such as electrogalvanized steel, hot-dip galvanized steel, galvanized and annealed steel, and zinc-alloy plated steel. Aluminum alloys of the 2XXX, 5XXX, 6XXX, and 7XXX series, as well as clad aluminum alloys and cast aluminum alloys of the A356 series, may also be used as the substrate. Magnesium alloys of the AZ31B, AZ91C, AM60B, or EV31A series may also be used as the substrate. The substrate used in the present invention may also comprise titanium and / or titanium alloys. Other suitable non-ferrous metals include copper and magnesium, as well as alloys of these materials.Suitable metal substrates for use in the present invention include those commonly used in the assembly of vehicle bodies (for example, but not limited to, doors, body panels, trunk lids, roof panels, hoods, roofs and / or stringers, rivets, landing gear components, and / or skins used in an aircraft), a vehicle frame, vehicle parts, motorcycles, wheels, industrial structures and components, such as household appliances, including washing machines, dryers, refrigerators, ovens, dishwashers, and the like, agricultural equipment, lawn and garden equipment, air conditioning units, heat pump units, garden furniture, and other articles. As used herein, "vehicle" or variations thereof include, but are not limited to, aircraft and / or land vehicles for civil, commercial, and military use, such as cars, motorcycles, and / or trucks.For example, the metal substrate may also be in the form of a metal sheet or a fabricated part. It is also understood that the substrate may be pretreated with a pretreatment solution, including a zinc phosphate pretreatment solution, such as, for example, those described in U.S. 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. Coating methods, coatings vs coated substrates

[0087] The present invention also relates to methods for coating a substrate, such as any of the electroconductive substrates mentioned above. According to the present invention, such a method may comprise electrophoretically applying an electrodepositable coating composition as described above onto at least a portion of the substrate and curing the coating composition to form an at least partially cured coating on the substrate. According to the present invention, the method may comprise (a) electrophoretically depositing an electrodepositable coating composition according to the present invention onto at least a portion of the substrate and (b) heating the coated substrate to a temperature and for a time sufficient to cure the electrodeposited coating on the substrate.According to the present invention, the method may optionally further comprise (c) applying directly to the at least partially cured electrodeposited coating one or more coating compositions containing pigments and / or one or more pigment-free coating compositions to form a topcoat over at least a portion of the at least partially cured electrodeposited coating and (d) heating the coated substrate from step (c) to a temperature and for a time sufficient to cure the topcoat.

[0088] According to the present invention, the cationic electrodepositable coating composition of the present invention can be deposited onto an electrically conductive substrate by placing the composition in contact with an electrically conductive cathode and an electrically conductive anode, wherein the surface to be coated is the cathode. Upon contact with the composition, an adherent film of the coating composition is deposited on the cathode when a sufficient voltage is applied between the electrodes. The conditions under which the electrodeposition is carried out are, in general, similar to those used in the electrodeposition of other types of coatings. The applied voltage can vary and can range, for example, from a level as low as one volt to one as high as several thousand volts, such as between 50 and 500 volts. The current density can be between 0.5 amperes and 15 amperes per square foot and tends to decrease during electrodeposition, indicating the formation of an insulating film.

[0089] After the cationic electrodepositable coating composition is electrodeposited onto at least a portion of the electroconductive substrate, the coated substrate is heated to a temperature and for a time sufficient to at least partially cure the electrodeposited coating onto the substrate. As used herein, the expression "at least partially cured with respect to a coating" refers to a coating formed by subjecting the coating composition to curing conditions such that a chemical reaction of at least a portion of the reactive groups of the components of the coating composition occurs to form a coating. The coated substrate may be heated to a temperature in the range of 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), or 300°F to 360°F (149°C to 180°C).The curing time may depend on the curing temperature as well as other variables, such as the thickness of the electrodeposited coating film, the level and type of catalyst present in the composition, and the like. For the purposes of the present invention, the only requirement is that the time be sufficient to cure the coating on the substrate. For example, the curing time may vary from 10 to 60 minutes, or from 20 to 40 minutes. The thickness of the resulting cured electrodeposited coating may vary from 15 to 50 micrometers.

[0090] According to the present invention, the anionic electrodepositable coating composition of the present invention can be deposited onto an electrically conductive substrate by placing the composition in contact with an electrically conductive cathode and an electrically conductive anode, wherein the surface to be coated is the anode. Upon contact with the composition, an adherent film of the coating composition is deposited on the anode when a sufficient voltage is applied between the electrodes. The conditions under which the electrodeposition is carried out are, in general, similar to those used in the electrodeposition of other types of coatings. The applied voltage can vary and can range, for example, from a level as low as one volt to one as high as several thousand volts, such as between 50 and 500 volts. The current density can be between 0.5 amperes and 15 amperes per square foot and tends to decrease during electrodeposition, indicating the formation of an insulating film.

[0091] After the anionic electrodepositable coating composition is electrodeposited onto at least a portion of the electroconductive substrate, the coated substrate may be heated to a temperature and for a time sufficient to at least partially cure the electrodeposited coating onto the substrate. As used herein, the expression "at least partially cured with respect to a coating" refers to a coating formed by subjecting the coating composition to curing conditions such that a chemical reaction of at least a portion of the reactive groups of the components of the coating composition occurs to form a coating. The coated substrate may be heated to a temperature in the range of 200°F to 450°F (93°C to 232.2°C), such as 275°F to 400°F (135°C to 204.4°C), or 300°F to 360°F (149°C to 180°C).The curing time may depend on the curing temperature as well as other variables, such as the thickness of the electrodeposited coating film, the level and type of catalyst present in the composition, and the like. For the purposes of the present invention, the only requirement is that the time be sufficient to cure the coating on the substrate. For example, the curing time may vary from 10 to 60 minutes, or from 20 to 40 minutes. The thickness of the resulting cured electrodeposited coating may vary from 15 to 50 micrometers.

[0092] If desired, the electrodepositable coating compositions of the present invention may also be applied to a substrate by non-electrophoretic coating application techniques, such as flow coating, dip coating, spray coating, and roller coating. For non-electrophoretic coating applications, the coating compositions may be applied to conductive substrates as well as non-conductive substrates, such as glass, wood, and plastic.

[0093] The present invention also relates to a coating formed by at least partially curing the electrodepositable coating composition described herein.

[0094] The present invention also relates to a substrate that is coated, at least in part, with the electrodepositable coating composition described herein in a at least partially cured state. Multilayer coating compounds

[0095] The electrodepositable coating compositions of the present invention can be used in an electroplating layer that is part of a multilayer coating composite comprising a substrate with various coating layers. The coating layers may include a pretreatment layer, such as a phosphate layer (e.g., zinc phosphate layer), an electroplating layer resulting from the aqueous resin dispersion of the present invention, and suitable topcoat layers (e.g., basecoat, clear topcoat, pigmented coating monolayer, and composite compositions of color plus transparency). Suitable topcoat layers are understood to include any of those known in the art, and each individually may be water-based, solvent-based, in the form of solid particles (i.e., a powder coating composition), or in the form of a powder slurry.The topcoat typically includes a film-forming polymer, a crosslinking material, and, if it is a basecoat or a single-layer colored coating, one or more pigments. According to the present invention, the primer layer is arranged between the electroplating layer and the basecoat layer. According to the present invention, one or more of the topcoat layers are applied over a substantially uncured underlying layer. For example, a clear topcoat may be applied over at least a portion of a substantially uncured (wet-on-wet) basecoat layer, and both layers may be cured simultaneously in a downstream process.

[0096] Furthermore, topcoats can be applied directly over the electrodepositable coating layer. In other words, the substrate lacks a primer layer. For example, a basecoat layer can be applied directly over at least a portion of the electrodepositable coating layer.

[0097] It shall be understood that topcoats may be applied over the underlying layer even if the underlying layer has not fully cured. For example, a clear coat may be applied over a basecoat even if the basecoat has not undergone a curing stage. Both layers can then be cured during the subsequent curing stage, thus eliminating the need to cure the basecoat and clear coat separately.

[0098] According to the present invention, additional ingredients, such as colorants and fillers, may be present in the various coating compositions from which the topcoats are produced. Any colorant and filler may be used. For example, the colorant may be added to the coating in any suitable form, such as particles, dispersions, solutions, and / or separate sheets. A single colorant or a mixture of two or more colorants may be used in the coatings of the present invention. It should be noted that, in general, the colorant may be present in a multilayer composite in a sufficient quantity to impart the desired property, visual effect, and / or color effect.

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

[0100] Example pigments and / or pigment compositions include, but are not limited to, crude dioxazine carbazole pigment, azo pigments, monoazo, disazo, naphthol AS, salt type (lagos), benzimidazolone, condensation, metal complexes, isoindolinone, isoindoline and polycyclic phthalocyanine, quinacridone, perylene, perinone, diketopyrrole pyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavantrone, pyrantrone, antantrone, dioxazine, triarylcarbonium, quinophthalone, diketopyrrole pyrrole red (DPP BO red), titanium dioxide, carbon black, zinc oxide, antimony oxide, etc., and UV opacifying pigments such as iron oxide, yellow or transparent red iron oxide, phthalocyanine blue, and mixtures thereof. The term pigment and the expression colored filler agent can be used interchangeably.

[0101] Example dyes include, but are not limited to, solvent-based and / or aqueous dyes such as acid dyes, azo dyes, basic dyes, direct dyes, disperse dyes, reactive dyes, solvent dyes, sulfur dyes, mordant dyes, e.g., bismuth vanadate, anthraquinone, perylene, aluminum, quinacridone, thiazole, thiazine, azo, indigoid, nitro, nitroso, oxazine, phthalocyanine, quinoline, stilbene, and triphenylmethane.

[0102] Example dyes include, but are not limited to, pigments dispersed in water-miscible or water-based carriers, such as AQUA-CHEM 896, available on the trade through Degussa, Inc., CHARISMA COLORANTS and MAXITONER INDUSTRIAL COLORANTS, available on the trade through Accurate Dispersions, a division of Eastman Chemical, Inc.

[0103] The colorant may be in the form of a dispersion, including, but not limited to, a nanoparticle dispersion. Nanoparticle dispersions may include one or more highly dispersed nanoparticle colorants and / or colorant particles that produce a desired visible color and / or opacity and / or visual effect. Nanoparticle dispersions may include colorants, such as pigments or dyes, having a particle size of less than 150 nm, such as less than 70 nm, or less than 30 nm. The nanoparticles may be produced by milling stock organic or inorganic pigments with milling media having a particle size of less than 0.5 mm. Examples of nanoparticle dispersions and methods for preparing them are identified in U.S. Patent No. 6,875,800 B2, which is incorporated herein by reference.Nanoparticle dispersions can also be produced by crystallization, precipitation, gas-phase condensation, and chemical weathering (i.e., partial dissolution). To minimize nanoparticle reagglomeration within the coating, a resin-coated nanoparticle dispersion can be used. As used herein, a resin-coated nanoparticle dispersion refers to a continuous phase in which separate composite microparticles comprising a nanoparticle and a resin coating on the nanoparticle are dispersed. Examples of resin-coated nanoparticle dispersions and methods for preparing them are identified in U.S. Patent Application No. 10 / 876,031 filed June 24, 2004, which is incorporated herein by reference, and U.S. Provisional Application No. 60 / 482,167 filed June 24, 2003, which is also incorporated herein by reference.

[0104] According to the present invention, special effect compositions that can be used in one or more layers of the multilayer coating compound include pigments and / or compositions that produce one or more appearance effects, such as reflectance, pearlescence, metallic luster, phosphorescence, fluorescence, photochromism, photosensitivity, thermochromism, goniochromism, and / or color change. Additional special effect compositions may provide other perceptible properties, such as reflectivity, opacity, or texture. For example, special effect compositions may produce a color change, such that the color of the coating changes when the coating is viewed from different angles. Example color effect compositions are identified in U.S. Patent No. 6,894,086, which is incorporated herein by reference.Additional color effect compositions may include transparent coated mica and / or synthetic mica, coated silica, coated alumina, a transparent liquid crystal pigment, a liquid crystal coating and / or any composition where interference occurs from a differential refractive index within the material and not because the differential refractive index is between the surface of the material and air.

[0105] According to the present invention, a photosensitive and / or photochromatic composition, which reversibly changes its color when exposed to one or more light sources, can be used in a number of layers in the multilayer composite. The photochromatic and / or photosensitive compositions can be activated by exposure to radiation of a specific wavelength. When the composition is excited, the molecular structure changes, and the altered structure exhibits a new color that is different from the original color of the composition. When the radiation exposure is removed, the photochromatic and / or photosensitive composition can return to a resting state, in which the original color of the composition returns. For example, the photochromatic and / or photosensitive composition may be colorless in a non-excited state and may exhibit a color in an excited state.A complete color change can occur within a period ranging from milliseconds to several minutes, such as 20 to 60 seconds. Example photochromic and / or photosensitive compositions include photochromic dyes.

[0106] According to the present invention, the photosensitive and / or photochromatic composition may be associated with and / or at least partially bonded to, such as by covalent bonding, a polymer and / or polymeric materials of a polymerizable component. Unlike some coatings in which the photosensitive composition may migrate out of the coating and crystallize on the substrate, the photosensitive and / or photochromatic composition associated with and / or at least partially bonded to a polymer and / or polymerizable component according to the present invention has minimal migration out of the coating. Examples of photosensitive and / or photochromatic compositions and methods for preparing them are identified in U.S. Patent Application No. 10 / 892,919, filed July 16, 2004, and incorporated herein by reference.

[0107] The electrodepositable coating composition of the present invention may also be substantially free, essentially free, or completely free of silicon dioxide microspheres and / or silicon dioxide nanospheres. As used herein, the electrodepositable coating composition is substantially free of silicon dioxide microspheres and / or silicon dioxide nanospheres if these are present in the electrodepositable coating composition, if at all, in an amount of less than 3% by weight, based on the total weight of the resin solids.As used herein, the electrodepositable coating composition is essentially free from silicon dioxide microspheres and / or silicon dioxide nanospheres if these are present in the electrodepositable coating composition, if at all, in an amount of less than 1% by weight, based on the total weight of the electrodepositable coating composition. As used herein, the electrodepositable coating composition is completely free from silicon dioxide microspheres and / or silicon dioxide nanospheres if these are not present in the electrodepositable coating composition, i.e., 0% by weight.

[0108] As used herein, unless otherwise stated, the substantially free expression μλ / iyy means that the component is present, if at all, in an amount of less than 5% by weight, based on the total weight of the suspension composition.

[0109] As used herein, unless otherwise stated, the term essentially free means that the component is present, if at all, in an amount of less than 1% by weight, based on the total weight of the suspension composition.

[0110] As used herein, unless otherwise stated, the term completely free means that the component is not present in the suspension composition, i.e., 0.00% by weight, based on the total weight of the suspension composition.

[0111] For the purposes of this detailed description, it is understood that the invention may assume variations and alternative sequences of steps, except where expressly stated otherwise. Furthermore, apart from any operational example, or where otherwise indicated, it is understood that all numbers expressing, for example, quantities of ingredients used in the specification and the claims are modified in all cases by the expression "around". Accordingly, unless otherwise stated, the numerical parameters stated in the following specification and the appended claims are approximations that may vary depending on the properties desired to be obtained with the present invention.At a minimum, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be interpreted at least in light of the number of significant digits reported and by applying customary rounding techniques.

[0112] Although the numerical parameters and ranges that establish the broad scope of the invention are approximations, the numerical values ​​stated in the specific examples are reported as accurately as possible. However, any numerical value inherently contains certain errors that necessarily result from the standard variation found in their respective test measurements.

[0113] Furthermore, it should be understood that any numerical range listed herein is intended to include all subranges within it. For example, a range from 1 to 10 is intended to include all subranges between (and inclusive of) the minimum value of 1 and the maximum value of 10; that is, it has a minimum value equal to or greater than 1 and a maximum value equal to or less than 10. [O114] As used herein, "which includes," "which contains," and similar expressions are understood in the context of this application to be synonymous with "comprising" and are therefore open-ended expressions and do not exclude the presence of additional undescribed or unlisted elements, materials, ingredients, or method steps. As used herein, "which consists of" is understood in the context of this application to exclude the presence of any unspecified element, ingredient, or method step. As used herein, "which essentially consists of" is understood in the context of this application to include the specified elements, materials, ingredients, or method steps and those that do not materially affect the basic and novel characteristics of what is being described. [O115] As used herein, the terms and expressions on, applied on, applied to, formed on, formed in, deposited on and deposited in mean formed, superimposed on, deposited or provided on the surface but not necessarily in contact with it. For example, a composition deposited on a substrate does not preclude the presence of one or more other intermediate coating layers of the same or a different composition between the electrodepositable coating composition and the substrate.

[0116] In this application, the use of the singular includes the plural and the plural includes the singular, unless specifically stated otherwise. For example, while reference is made herein to an acrylic polymer, a film-forming polymer containing an ionic salt group different from the acrylic polymer, a hydroxy-functional (meth)acrylate monomer, and a hydroxy-functional (meth)acrylamide monomer, a combination (i.e., a plurality) of these components may be used. Furthermore, in this application, the use of "or" means "and / or" unless specifically stated otherwise, although "and / or" may be explicitly used in certain instances.

[0117] Although specific aspects of the invention have been described in detail, persons of a middling skill will appreciate that various modifications and alternatives to these details could be developed in light of the general lessons of the disclosure. Accordingly, the particular provisions disclosed are intended only to be illustrative and do not limit the scope of the invention, which is fully expressed in the appended claims and all their equivalents.

[0118] In view of the foregoing, the present invention relates, in particular, without limitation, to the following aspects: [O119] Aspect 1. An electrodepositable coating composition comprising: (a) an acrylic polymer comprising more than 60% by weight of constituent units comprising the residue of a hydroxyl-functional (meth)acrylate monomer and / or a hydroxyl-functional (meth)acrylamide monomer, based on the total weight of the acrylic polymer; and (b) a film-forming polymer containing an ionic salt group other than the acrylic polymer. ma / iyy [O12O] Aspect 2. The electrodepositable coating composition of aspect 1 above, wherein the constitutional units comprising the hydroxy-functional (meth)acrylate monomer residue may be present in the acrylic polymer in an amount of 61% to 100% by weight, such as 70% to 100% by weight, such as 80% to 100% by weight, such as 90% to 100% by weight, such as 93% to 100% by weight, such as 95% to 100% by weight, such as 97% to 100% by weight, such as 61% to 97% by weight, such as 70% to 97% by weight, such as 80% to 97% by weight, such as 90% to 97% by weight, such as 93% to 97% by weight, such as 95% to 97% by weight, such as 61% to 95% by weight, such as 70% to 95% by weight, such as 80% to 95% by weight, such as 90% to 95% by weight, such as 93% to 95% by weight, such as 61% to 90% by weight, such as 70% to 90% by weight, such as 80% to 90% by weight, 61% to 85% by weight, such as 70% to 85% by weight, such as 80% to 85% by weight, 61% to 75% by weight, such as 70% to 75% by weight,such as 61% to 70% by weight, depending on the total weight of the acrylic polymer. [O121] Aspect 3. The electrodepositable coating composition according to any of the above aspects, wherein the hydroxyfunctional (meth)acrylate monomer comprises a Ci to Cio hydroxyalkyl (meth)acrylate, a Ci to Cs hydroxyalkyl (meth)acrylate, a Ci to C3 hydroxyalkyl (meth)acrylate, or combinations thereof. [O122] Aspect 4. The electrodepositable coating composition according to any of the above aspects, wherein the hydroxyl functional (meth)acrylate monomer comprises hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate or combinations thereof. [O123] Aspect 5. The electrodepositable coating composition according to any of the above aspects, wherein the constitutional units comprising the hydroxy-functional (meth)acrylamide monomer residue may be present in the acrylic polymer in an amount of 61% to 100% by weight, such as 70% to 100% by weight, such as 80% to 100% by weight, such as 90% to 100% by weight, such as 93% to 100% by weight, such as 95% to 100% by weight, such as 97% to 100% by weight, such as 61% to 97% by weight, such as 70% to 97% by weight, such as 80% to 97% by weight, such as 90% to 97% by weight, such as 93% to 97% by weight, such as 95% to 97% by weight, such as 61% to 95% by weight, such as 70% to 95% by weight, such as 80% to 95% by weight, such as 90% to 95% by weight, such as 93% to 95% by weight, such as 61% to 90% by weight, such as 70% to 90% by weight, such as 80% to 90% by weight, 61% to 85% by weight, such as 70% to 85% by weight, such as 80% to 85% by weight, 61% to 75% by weight,such as 70% to 75% by weight, such as 61% to 70% by weight, depending on the total weight of the acrylic polymer. [O124] Aspect 6. The electrodepositable coating composition of μλ / t / zuzz / uzo 1 yy in accordance with any of the above aspects, wherein the hydroxy-functional (meth)acrylamide monomer comprises a Ci to Cio hydroxyalkyl (meth)acrylamide, a Ci to Cs hydroxyalkyl (meth)acrylamide, a Ci to C3 hydroxyalkyl (meth)acrylamide, or combinations thereof. [O125] Aspect 7. The electrodepositable coating composition according to any of the above aspects, wherein the hydroxyl-functional (meth)acrylamide monomer comprises hydroxymethyl (meth)acrylamide, hydroxyethyl (meth)acrylamide, or combinations thereof. [O126] Aspect 8. The electrodepositable coating composition according to any of the above aspects, wherein the acrylic polymer further comprises constitutional units comprising the residue of a Ci-Cis alkyl (meth)acrylate monomer. [O127] Aspect 9. The electrodepositable coating composition according to aspect 8, wherein the constitutional units comprising the residue of Ci-Cisalkyl (meth)acrylates are present in the acrylic polymer in an amount of up to 39% by weight, such as 1% to 30% by weight, such as 1% to 20% by weight, such as 1% to 10% by weight, such as 2% to 8% by weight, such as 3% to 6% by weight, depending on the total weight of the acrylic polymer. [O128] Aspect 10. The electrodepositable coating composition according to any of the above aspects, wherein the acrylic polymer further comprises constitutional units comprising the residue of an ethylenically unsaturated amino-functional monomer [O129] Aspect 11. The electrodepositable coating composition according to aspect 10, wherein the ethylenically unsaturated amino-functional monomer comprises 2-(dimethylamino)ethyl methacrylate f'DMAEMA), 2-(dimethylamino)ethyl acrylate, 3-(dimethylamino)propyl (meth)acrylate, 2-(diethylamino)ethyl (meth)acrylate, 2-(tert-butylamino)ethyl (meth)acrylate and 2-(diethylamino)ethyl (meth)acrylate, or combinations thereof. [O13O] Aspect 12. The electrodepositable coating composition according to aspect 10 or 11, wherein the constitutional units comprising the amino-functional monomer residue may be present in the acrylic polymer in an amount of up to 39% by weight, such as 1% to 30% by weight, such as 1% to 20% by weight, such as 1% to 10% by weight, such as 2% to 8% by weight, such as 3% to 6% by weight, depending on the total weight of the acrylic polymer. [O131] Aspect 13. The electrodepositable coating composition according to any of the above aspects, wherein the acrylic polymer further comprises constitutional units comprising the residue of an aromatic vinyl compound. ma / t / zuzz / uzo 1 yy [O132] Aspect 14. The electrodepositable coating composition according to aspect 13, wherein the aromatic vinyl compound comprises styrene, alpha-methylstyrene, alpha-chloromethylstyrene, vinyl toluene, or combinations thereof. [O133] Aspect 15. The electrodepositable coating composition according to aspect 13 or 14, wherein the constitutional units comprising the residue of the aromatic vinyl compound may be present in the acrylic polymer in an amount of up to 39% by weight, such as 1% to 30% by weight, such as 1% to 20% by weight, such as 1% to 10% by weight, such as 2% to 8% by weight, such as 3% to 6% by weight, depending on the total weight of the acrylic polymer. [O134] Aspect 16. The electrodepositable coating composition according to any of the above aspects, wherein the acrylic polymer further comprises constitutional units comprising the residue of an ethylenically unsaturated epoxide-functional monomer. [O135] Aspect 17. The electrodepositable coating composition according to aspect 16, wherein the ethylenically unsaturated epoxide-functional monomer comprises glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl(meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl(meth)acrylate, allyl glycidyl ether, or combinations thereof. [O136] Aspect 18. The electrodepositable coating composition according to aspect 16 or 17, wherein the constitutional units comprising the ethylene-unsaturated epoxide-functional monomer residue may be present in the acrylic polymer in an amount of up to 39% by weight, such as 1% to 30% by weight, such as 1% to 20% by weight, such as 1% to 10% by weight, such as 2% to 8% by weight, such as 3% to 6% by weight, depending on the total weight of the acrylic polymer. [O137] Aspect 19. The electrodepositable coating composition according to any of the above aspects, wherein the acrylic polymer further comprises constitutional units comprising the residue of an ethylenically unsaturated acid-functional monomer. [O138] Aspect 20. The electrodepositable coating composition according to aspect 19, wherein the ethylenically unsaturated functional acid monomer comprises ethylenically unsaturated phosphoric acid functional monomers or carboxylic acid functional monomers. [O139] Aspect 21. The electrodepositable coating composition according to aspect 19 or 20, wherein the constitutional units comprising the ethylenically unsaturated functional acid monomer residue may be present in the acrylic polymer in an amount of up to 39% by weight, such as from 1% to 30% by weight, such as from 1% to 20% by weight, such as 1% to 10% by weight, such as 2% to 8% by weight, such as 3% to 6% by weight, depending on the total weight of the acrylic polymer. [O14O] Aspect 22. The electrodepositable coating composition according to any of the above aspects, wherein the acrylic polymer further comprises constitutional units comprising the residue of a monomer comprising two or more ethylenically unsaturated groups per molecule. [O141] Aspect 23. The electrodepositable coating composition according to aspect 22, wherein the monomer comprising two or more ethylenically unsaturated groups per molecule comprises ethylene glycol dimethacrylate, allyl methacrylate, hexanediol diacrylate, methacrylic anhydride, tetraethylene glycol diacrylate and / or tripropylene glycol diacrylate, ethoxylated trimethylolpropane triacrylate having 0 to 20 ethoxy units, [ethoxylated] trimethylolpropane trimemethacrylate having 0 to 20 ethoxy units, di-pentaerythritol triacrylate, pentaerythritol tetraacrylate and / or di-pentaerythritol pentaacrylate. [O142] Aspect 24. The electrodepositable coating composition according to aspect 22 or 23, wherein the constitutional units comprising the monomer residue comprising two or more ethylenically unsaturated groups per molecule may be present in the acrylic polymer in an amount of 15% by weight, such as 0.1% to 10% by weight, such as 0.1% to 5% by weight, depending on the total weight of the acrylic polymer. [O143] Aspect 25. The electrodepositable coating composition according to any of the above aspects, wherein the acrylic polymer further comprises constitutional units comprising the residue of an ethylenically unsaturated amide-functional monomer not including a hydroxyl group. [O144] Aspect 26. The electrodepositable coating composition according to aspect 25, wherein the ethylenically unsaturated amide-functional monomer comprises acrylamide, (meth)acrylamide, substituted N-alkyl (meth)acrylamides, or combinations thereof. [O145] Aspect 27. The electrodepositable coating composition according to aspect 25 or 26, wherein the constitutional units comprising the ethylene-unsaturated amide-functional monomer residue may be present in the acrylic polymer in an amount of up to 39% by weight, such as 1% to 30% by weight, such as 1% to 20% by weight, such as 1% to 10% by weight, such as 2% to 8% by weight, such as 3% to 6% by weight, depending on the total weight of the acrylic polymer. [O146] Aspect 28. The electrodepositable coating composition according to any of the above aspects, wherein the acrylic polymer further comprises constitutional units comprising the residue of other ethylenically ma / iyy unsaturated hydroxy-functional monomers that are not (meth)acrylates or (meth)acrylamides. [O147] Aspect 29. The electrodepositable coating composition according to aspect 28, wherein the other ethylenically unsaturated hydroxyfunctional monomers that are not (meth)acrylates or (meth)acrylamides comprise vinyl alcohol. [O148] Aspect 30. The electrodepositable coating composition according to aspect 25 or 26, wherein the constitutional units comprising the residue of the other ethylenically unsaturated hydroxyl-functional monomers that are not (meth)acrylates or (meth)acrylamides may be present in the acrylic polymer in an amount of up to 39% by weight, such as 1% to 30% by weight, such as 1% to 20% by weight, such as 1% to 10% by weight, such as 2% to 8% by weight, such as 3% to 6% by weight, depending on the total weight of the acrylic polymer. [O149] Aspect 31. The electrodepositable coating composition according to any of the above aspects, wherein the acrylic polymer further comprises constitutional units comprising the residue of ethylenically unsaturated thiol-functional monomers, ethylenically unsaturated carbamate-functional monomers, or combinations thereof. [O15O] Aspect 32. The electrodepositable coating composition according to any of the above aspects, wherein the acrylic polymer comprises a primary hydroxyl group, secondary hydroxyl groups, a tertiary hydroxyl group or combinations thereof. [O151] Aspect 33. The electrodepositable coating composition according to aspect 32, wherein the acrylic polymer further comprises thiol groups, amide groups, carbamate groups, primary amino groups and / or secondary amino groups. [O152] Aspect 34. The electrodepositable coating composition according to any of the above aspects, wherein the acrylic polymer has a theoretical hydroxyl equivalent weight of at least 100 g / OH to 500 g / OH, such as 100 g / OH to 400 g / OH, such as 100 g / OH to 300 g / OH, such as 100 g / OH to 200 g / OH, such as 100 g / OH to 150 g / OH, such as 100 g / OH to 140 g / OH, such as 100 g / OH to 130 g / OH, such as 110 g / OH to 500 g / OH, such as 110 g / OH to 400 g / OH, such as 110 g / OH to 300 g / OH, such as 110 g / OH to 200 g / OH, such as from 110 g / OH to 150 g / OH, such as from 110 g / OH to 140 g / OH, such as from 110 g / OH to 130 g / OH, such as from 120 g / OH to 500 g / OH, such as from 120 g / OH to 400 g / OH, such as from 120 g / OH to 300 g / OH, such as from 120 g / OH to 200 g / OH, such as from 120 g / OH to 150 g / OH, such as from 120 g / OH to 140 g / OH, such as from 120 g / OH to 130 g / OH, such as from 140 g / OH to 500 g / OH, such as from 140 g / OH to 400 g / OH, such as from 140 g / OH at 300 g / OH,such as from 140 g / OH to 200 g / OH, such as from 140 g / OH to 150 g / OH. ma / iyy [O153] Aspect 35. The electrodepositable coating composition according to any of the above aspects, wherein the acrylic polymer has a theoretical hydroxyl value of 100 to 600 mg KOH / gram of acrylic polymer, such as 250 to 600 mg KOH / gram of acrylic polymer, such as 400 to 600 mg KOH / gram of acrylic polymer, such as 500 to 600 mg KOH / gram of acrylic polymer, such as 100 to 500 mg KOH / gram of acrylic polymer, such as 250 to 500 mg KOH / gram of acrylic polymer, such as 400 to 500 mg KOH / gram of acrylic polymer, 100 to 400 mg KOH / gram of acrylic polymer, such as 250 to 400 mg KOH / gram of acrylic polymer, 100 to 300 mg KOH / gram of acrylic polymer acrylic, such as 250 to 300 mg KOH / gram of acrylic polymer. [O154] Aspect 36. The electrodepositable coating composition according to any of the above aspects, wherein (a) the acrylic polymer has a z-average molecular weight of 500,000 to 600,000,000 g / mol, such as 500,000 to 60,000,000 g / mol, such as 500,000 to 50,000,000 g / mol, such as 500,000 to 35,000,000 g / mol, such as 500,000 to 20,000,000 g / mol, such as 500,000 to 10,000,000 g / mol, such as 500,000 to 4,000,000 g / mol, such as 500,000 to 3,500,000 g / mol, such as 500,000 to 3,000,000 g / mol, such as 1,000,000 to 600,000,000 g / mol, such as 1,000,000 to 60,000,000 g / mol, such as 1,000,000 to 50,000,000 g / mol, such as 1,000,000 to 35,000,000 g / mol, such as 1,000,000 to 20,000,000 g / mol, such as 1,000,000 to 10,000,000 g / mol, such as 1,000,000 to 4,000,000 g / mol, such as 1,000,000 to 3,500,000 g / mol, such as 1,000,000 to 3,000,000 g / mol, such as 1,400,000 to 600,000,000 g / mol, such as 1,400,000 to 60,000,000 g / mol, such as 1,400,000 to 50,000,000 g / mol, such as 1,400,000 to 35,000,000 g / mol, such as 1,400,000 to 20,000,000 g / mol, such as 1,400,000 to 10,000,000 g / mol, such as 1,400,000 to 4,000,000 g / mol, such as 1,400,000 to 3,500,000 g / mol, such as 1,400,000 to 3,000,000 g / mol, such as 1,750,000 to 600,000,000 g / mol, such as 1,750,000 to 60,000,000 g / mol, such as 1,750,000 to 50,000,000 g / mol, such as 1,750,000 to 35,000,000 g / mol, such as 1,750,000 to 20,000,000 g / mol, such as 1,750,000 to 10,000,000 g / mol, such as 1,750,000 to 4,000,000 g / mol, such as 1,750,000 to 3,500,000 g / mol, such as 1,750,000 to 3,000,000 g / mol, such as 2,000,000 to 600,000,000 g / mol, such as 2,000,000 to 60,000,000 g / mol, such as 2,000,000 to 50,000,000 g / mol, such as 2,000,000 to 35,000,000 g / mol, such as 2,000,000 to 20,000,000 g / mol, such as 2,000,000 to 10,000,000 g / mol, such as 2,000,000 to 4,000,000 g / mol, such as 2,000,000 to 3,500,000 g / mol, such as 2,000,000 to 3,000,000 g / mol, such as 2,500,000 to 600,000,000 g / mol, such as 2,500,000 to 60,000,000 g / mol,such as 2,500,000 to 50,000,000 g / mol, such as 2,500,000 to 35,000,000 g / mol, such as 2,500,000 to 20,000,000 g / mol, such as 2,500,000 to 10,000,000 g / mol, such as 2,500,000 to 4,000,000 g / mol, such as 2,500,000 to 3,500,000 g / mol, such as 2,500,000 to 3,000,000 g / mol, and / or (b) the acrylic polymer has an average molecular weight of 200,000 to 1,600,000 g / mol, such as 200,000 to 1,200,000 g / mol, such as ma / iyy, 200,000 to 1,100,000 g / mol, such as 200,000 to 900,000 g / mol, such as 200,000 to 800,000 g / mol, such as 400,000 to 1,600,000 g / mol, such as 400,000 to 1,200,000 g / mol, such as 400,000 to 1,100,000 g / mol, such as 400,000 to 900,000 g / mol, such as 400,000 to 800,000 g / mol, such as 500,000 to 1,600,000 g / mol, such as 500,000 to 1,200,000 g / mol, such as 500,000 to 1,100,000 g / mol, such as 500,000 to 900,000 g / mol, such as 500,000 to 800,000 g / mol. [O155] Aspect 37. The electrodepositable coating composition according to any of the above aspects, wherein the acrylic polymer comprises a linear polymer, a branched polymer and / or a crosslinked polymer network. [O156] Aspect 38. The electrodepositable coating composition according to any of the above aspects, wherein the acrylic polymer is substantially free, essentially free or completely free of constitutional units comprising diene monomer residue. [O157] Aspect 39. The electrodepositable coating composition according to any of the above aspects, wherein the acrylic polymer is substantially free, essentially free or completely free of constitutional units comprising the residue of isobutylene monomers. [O158] Aspect 40. The electrodepositable coating composition according to any of the above aspects, wherein the acrylic polymer is substantially free, essentially free or completely free of constitutional units comprising residue of nitrogen-containing monomers, constitutional units comprising residue of vinyl alcohol and / or residue of a polymeric dispersant. [O159] Aspect 41. The electrodepositable coating composition according to any of the above aspects, wherein the acrylic polymer is substantially free, essentially free, or completely free of constitutional units comprising the residue of monomers comprising three or more ethylenically unsaturated groups per molecule. [O16O] Aspect 42. The electrodepositable coating composition according to any of the above aspects, wherein the acrylic polymer is substantially free, essentially free or completely free of silicon. [O161] Aspect 43. The electrodepositable coating composition according to any of the above aspects, wherein the acrylic polymer comprises a single-stage acrylic polymer. [O162] Aspect 44. The electrodepositable coating composition according to any of the above aspects, wherein the acrylic polymer is present in the electrodepositable coating composition in an amount of 0.05% to 10% by weight, such as 0.1% to 10% by weight, such as 0.2% to 10% by weight, such as 0.4% to 10% by weight, such as 0.5% to 10% by weight, such as 1% to 10% by weight, such as 0.05% to 3% by weight, such as 0.1% to 3% by weight, such as 0.2% to 3% by weight, such as 0.4% to 3% by weight, such as 0.5% to 3% by weight, such as 1% to 3% by weight, such as 0.05% to 2% by weight, such as 0.1% to 2% by weight, such as 0.2% to 2% by weight, such as 0.4% to 2% by weight, such as 0.5% to 2% by weight, such as 1% to 2% by weight, such as 0.5% to 1% by weight, such as 0.1% to 1% by weight, such as 0.2% to 1% by weight, such as 0.4% to 1% by weight, 0.5% to 1% by weight, such as 0.05% to 0.85% by weight, such as 0.1% to 0.85% by weight, 0.2% to 0.85% by weight, such as 0.4% to 0.85% by weight, such as 0.5% to 0.85% by weight, depending on the total weight of resin solids in the electrodepositable coating composition. [O163] Aspect 45. The electrodepositable coating composition according to any of the above aspects, wherein the film-forming polymer containing an ionic salt group comprises a film-forming polymer containing a cationic salt group. [O164] Aspect 46. The electrodepositable coating composition according to any of the above aspects 1 to 44, wherein the film-forming polymer containing an ionic salt group comprises a film-forming polymer containing an anionic salt group. [O165] Aspect 47. The electrodepositable coating composition according to any of the above aspects, wherein the film-forming polymer containing an ionic salt group comprises active hydrogen functional groups. [O166] Aspect 48. The electrodepositable coating composition according to any of the above aspects, wherein the electrodepositable coating composition further comprises a curing agent. [O167] Aspect 49. The electrodepositable coating composition according to aspect 48, wherein the curing agent comprises reactive functional groups with active hydrogen functional groups. [O168] Aspect 50. The electrodepositable coating composition according to aspects 48 or 49, wherein the curing agent comprises aminoplast resins, phenolic resins, at least partially blocked polyisocyanates, or combinations thereof. [O169] Aspect 51. The electrodepositable coating composition according to any of aspects 48-50, wherein the curing agent is present in the electrodepositable coating composition in an amount of 10% to 60% by weight, depending on the total weight of the resin solids of the electrodepositable coating composition. [O17O] Aspect 52. The electrodepositable coating composition of μλ / iyy in accordance with any of the above aspects, wherein the film-forming polymer containing an ionic salt group is present in the electrodepositable coating composition in an amount of 40% to 90% by weight, depending on the total weight of the resin solids of the electrodepositable coating composition. [O171] Aspect 53. The electrodepositable coating composition according to any of the above aspects further comprising a poly(I)-iquilene oxide polymer. [O172] Aspect 54. The electrodepositable coating composition according to any of the above aspects, wherein the electrodepositable coating composition is substantially free, essentially free or completely free of silicon dioxide microspheres and / or silicon dioxide nanospheres. [O173] Aspect 55. A method for coating a substrate comprising electrophoretically applying a coating deposited from an electrodepositable coating composition according to any of the above aspects 1 to 54 onto at least a portion of the substrate. [O174] Aspect 56. A coating at least partially cured formed by at least partially curing a coating deposited from an electrodepositable coating composition in accordance with any of the above aspects 1 to 54. [O175] Aspect 57. A substrate comprising a coating deposited from the electrodepositable coating composition according to any of the above aspects 1 to 54 on at least a portion of the substrate. [O176] Aspect 58. The substrate according to aspect 57, wherein the coating has a 20° reduction in gloss value of at least 20%, such as at least 40%, such as at least 50%, such as at least 60%, when the acrylic polymer is present in the electrodepositable coating composition in an amount of 0.5% by weight based on the total resin solids, the gloss values ​​measured with a BYK-Gardner Hazemeter (Catalog No. 4601) in accordance with ASTM D523, and the reduction in gloss value compared to a substrate coated with a comparative electrodepositable coating composition that does not include the acrylic polymer but is otherwise the same composition as the electrodepositable coating composition. [O177] Aspect 59. The substrate according to aspect 57 or 58, wherein the coating has a 60° gloss value reduction of at least 10%, such as at least 20%, such as at least 25%, such as at least 30%, such as at least 40%, when the acrylic polymer is present in the electrodepositable coating composition in an amount of 0.5% by weight based on the total resin solids, the gloss values ​​measured with BYK ma / iyy Gardner Hazemeter (Catalog No. 4601) in accordance with ASTM D523 and the reduction of the gloss value compared to a substrate coated with a comparative electrodepositable coating composition that does not include the acrylic polymer but otherwise has the same composition as the electrodepositable coating composition. [O178] Aspect 60. The substrate in accordance with any of aspects 57 to 59, wherein the average edge coverage percentage of the coated substrate is improved by at least 20%, such as at least 40%, such as at least 60%, as measured according to the drill edge coverage test method, compared to a substrate coated with a comparative electrodepositable coating composition that does not include the acrylic polymer but otherwise has the same composition as the electrodepositable coating composition.

[0179] The following examples illustrate the invention, but do not limit the invention to their details. Unless otherwise indicated, all parts and percentages in the following examples, as well as throughout the specification, are by weight. EXAMPLES μλ / iyy Example 1: Experimental synthesis of acrylic polymer A Table 1 Charge No. Material Quantity (g) 1 Deionized water 1737.695 2 2-Hydroxyethyl acrylate 110.917 3 Deionized water 53.550 Hydrogen peroxide (35% in deionized water) 1.702 4 Isoascorbic acid 0.309 Ferrous ammonium sulfate 0.003 Deionized water 68.811 5 Deionized water 14.045 Hydrogen peroxide (35% in deionized water) 0.048 6 Isoascorbic acid 0.048 Deionized water 14.248

[0180] An aqueous solution of an experimental acrylic polymer A was obtained according to the formulation disclosed in Table 1. To prepare the dispersion, charge 1 was added to a four-necked flask fitted with a thermocouple, nitrogen spray, and mechanical stirrer. The flask was heated to 25°C under a nitrogen blanket with rigorous stirring. At 25°C, the solution was sprayed with nitrogen for an additional 30 minutes. Charge 2 was then added to the reaction vessel after 10 minutes. Charge 3 was then introduced into the reaction vessel after... 2-3 minutes. Charge 4 was mixed and added using an addition funnel after 30 minutes. The reaction was allowed to continue exothermically during the addition. Once the addition was complete, the reactor was heated to 50°C and held at that temperature for 30 minutes. Charges 5 and 6 were then added dropwise, and the mixture was held at 50°C for 30 minutes. The reaction was then cooled to room temperature.

[0181] The solids content of the resulting aqueous acrylic polymer solution was determined by adding a quantity of reaction product to a tared aluminum plate, recording the weight of the dispersion and the plate, heating the test sample on the plate for 60 minutes at 110°C in an oven, allowing the plate to cool, reweighing the plate to determine the amount of remaining non-volatile content, and determining the solids content by dividing the weight of the non-volatile content by the weight of the total sample and multiplying by 100. This procedure was used to determine the solids content in each of the examples below. The resulting aqueous solutions of the acrylic polymers had a solids content of 5.50% by weight.

[0182] Weight average molecular weight (Mw) and z-average molecular weight (Mz) were determined by gel permeation chromatography (GPC). For polymers having a z-average molecular weight of less than 900,000, GPC was performed using a Waters 2695 separation module with a Waters 410 differential refractometer (RI detector), polystyrene standards having molecular weights from about 500 g / mol to 900,000 g / mol, dimethylformamide (DMF) with 0.05 M lithium bromide (LiBr) as the eluent at a flow rate of 0.5 mL / min, and an Asahipak GF-510 HQ column for separation. Regarding polymers having an average molecular weight at z (Mz) of more than 900,000 g / mol, GPC was performed using a Waters 2695 separation module with a Waters 410 differential refractometer (RI detector), polystyrene standards having molecular weights from around 500 g / mol to 3,000,000 g / mol, dimethylformamide (DMF) with 0.0.5 M lithium bromide (LiBr) was used as the eluent at a flow rate of 0.5 mL / min, and an Asahipak GF-7M HQ column was used for the separation. This procedure was followed for all molecular weight measurements included in the Examples. The resulting acrylic polymer A had an average molecular weight of 779,281 g / mol and an average molecular weight at z of 3,177,215 g / mol. μλ / t / zuzz / uzo ι yy Example 2: Experimental synthesis of acrylic polymer B Table 2 Charge No. Material Quantity (g) 1 Deionized water 522.615 2 2-Hydroxyethyl acrylate 30.023 3-Hydroxypropyl acrylate 3.336 3 Deionized water 16.105 Hydrogen peroxide (35% in deionized water) 0.512 4 Isoascorbic acid 0.093 Ferrous ammonium sulfate 0.001 Deionized water 20.695 5 Deionized water 4.224 Hydrogen peroxide (35% in deionized water) 0.014 6 Isoascorbic acid 0.014 Deionized water 4.285 ma / t / zuzz / uzo ι yy

[0183] An aqueous solution of an experimental acrylic polymer B was obtained according to the formulation disclosed in Table 2 and by following the same procedure described in Example 1.

[0184] The measured solids content of the resulting aqueous acrylic polymer B was 5.67% by weight. The average molecular weight of acrylic polymer B was 1,016,552 g / mol and the average molecular weight at z of acrylic polymer B was 9,752,124 g / mol, as measured according to the method described in Example 1. Example 3: Experimental synthesis of acrylic polymer C Table 3 Charge No. Material Quantity (g) 1 Deionized water 522.615 2 2-Hydroxyethyl acrylate 16.679 Hydroxymethyl acrylamide 16.679 3 Deionized water 16.105 Hydrogen peroxide (35% in deionized water) 0.512 4 Isoascorbic acid 0.093 Ferrous ammonium sulfate 0.001 Deionized water 20.695 5 Deionized water 4.224 Hydrogen peroxide (35% in deionized water) 0.014 6 Isoascorbic acid 0.014 Deionized water 4.285

[0185] An aqueous solution of an experimental acrylic polymer C was obtained according to the formulation disclosed in Table 3 and by following the same procedure described in Example 1.

[0186] The measured solids content of the resulting aqueous acrylic polymer C was 5.59% by weight. The weight average molecular weight of acrylic polymer C was 4,372,395 g / mol and the z-average molecular weight of acrylic polymer C was 54,329,274 g / mol, as measured according to the method described in Example 1. ma / 1 yy Example 4: Experimental synthesis of acrylic polymer D Table 4 Charge No. Material Quantity (g) 1 Deionized water 464.095 2-(dimethylamino)ethyl methacrylate 4.170 2 Formic acid 1.628 3 2-Hydroxyethyl acrylate 79.226 4 Deionized water 35.810 Hydrogen peroxide (35% in deionized water) 5.120 5 Isoascorbic acid 0.464 Ferrous ammonium sulfate 0.0025 Deionized water 19.482 6 Deionized water 4.352 Hydrogen peroxide (35% in deionized water) 0.036 7 Isoascorbic acid 0.072 Deionized water 4.380

[0187] An aqueous solution of an experimental acrylic polymer D was obtained according to the formulation disclosed in Table 4. To prepare the dispersion, charge 1 was added to a four-necked flask fitted with a thermocouple, nitrogen sprayer, and mechanical stirrer. Under a nitrogen blanket and with rigorous stirring, charge 2 was introduced dropwise, and the flask was heated to 25°C. At 25°C, the solution was sprayed with nitrogen for approximately 30 minutes. Charge 3 was added to the reaction vessel after 10 minutes. Charge 4 was introduced to the reaction vessel after 2–3 minutes. Charge 5 was mixed in and added using an addition funnel after 30 minutes. The reaction was allowed to become exothermic during the addition. After the addition was complete, the reactor was heated to 50°C and held at that temperature for 30 minutes. Loads 6 and 7 were added dropwise and the mixture was kept at 50°C for 30 minutes.The reaction was then cooled to room temperature.

[0188] The measured solids content of the resulting aqueous acrylic polymer D was 14.32 wt%. The weight average molecular weight of acrylic polymer D was 1,161,479 g / mol and the z-average molecular weight of acrylic polymer D was 22,608,042 g / mol, as measured according to the method described in Example 1. Example 5: Preparation of cationic resin E Table 5 Load No. Material Quantity (g) 1 DER 7321 640.7 2 Bisphenol A 155.2 3 Butylcarbitol formal2 7.96 4 Benzyldimethylamine 1.50 5 Butylcarbitol formal2 3.12 6 Butylcarbitol formal2 49.5 7 JEFFAMINE D4003 160.5 8 Butylcarbitol formal2 7.96 9 Bisphenol A4 diglycidyl ether 17.4 10 Butylcarbitol formal2 6.20 Used resin from reaction product of materials 1-10 913.5 11 Deionized water 1065.8 12 Lactic acid (88%) 47.8 13 Coco-amine ethoxylated surfactant 5 59.3 14 Deionized water 1243.7 1Aliphatic epoxy resin available through Dow Chemical Co. 2Available as MAZON 1651 through BASF Corporation. 3A polypropylene oxide resin terminated with primary amines available through Huntsman Corp. 4Available through Hexion Corporation as EPON 828. 5Available through Solvay as Rhodameen C5.

[0189] Loads 1, 2, and 3 were loaded into a three-liter round-bottom flask fitted with a stirrer and a temperature probe, and covered with nitrogen. The mixture was heated to 130°C. Loads 4 and 5 were mixed together and added to the mixture with the heater off. The mixture underwent an exothermic reaction up to 135°C, and heat was added as needed to maintain the temperature at 135°C for approximately two hours. The epoxide equivalent weight was checked every 30 minutes, and its increase was plotted over time. Heating continued at 135°C for the extrapolated time required for the epoxide equivalent weight of the mixture to reach 1.232 g / epoxide group. The heat was removed, load 6 was added, and the mixture was allowed to cool to 100°C for approximately 20 minutes with stirring. Then, load 7 was added and immediately followed by load 8 to rinse the line in the reactor.Following the exothermic reaction, heat was applied to maintain the reaction temperature at 95°C until the Gardner-Holdt viscosity of a sample of resin diluted 50 / 50 in methoxypropanol was L. A mixture of charges 9 and 10 was added, and the mixture was maintained at 95°C until the Gardner-Holdt viscosity of a sample of the resin diluted 50 / 50 in methoxypropanol was PQ. 913.5 g of this resin were poured into a mixture of 1,065.8 g of deionized water and 47.8 g of an 88% lactic acid solution in water at room temperature and mixed for 45 minutes. Charge 13 was added, and the mixture was stirred for 40 minutes at room temperature. Then, 1243.7 g of deionized water were added, and the mixture was stirred for an additional three hours at room temperature. The final aqueous dispersion had a measured solids content of 30.5% by weight, as determined using the method described in Example 1. Example 6: Preparation of cationic resin F: Main film-forming resin

[0190] This example describes the preparation of a cationic epoxy resin, used as the main film-forming resin, from a mixture of the following ingredients: Preparation of the curing agent for the blocked polyisocyanate Table 6 ma / iyy Charge No. Material Quantity (g) 1 Dibutyltin dilaurate 1.3 2 Ethylene glycol monobutyl ether 945.44 3 Diethylene glycol monobutyl ether 324.46 4 Methyl isobutyl ketone (MIBK) 15.52 5 Polymeric MDI polyisocyanate 1340.00 6 Methyl isobutyl ketone (MIBK) 307.05 1Rubinate M, available from Huntsman Corporation.

[0191] Charges 1, 2, 3, and 4 were added to a four-necked round-bottom flask fitted with a stirrer and a temperature probe, and covered with nitrogen. The temperature of the mixture was raised to 30°C. Charge 5 was then added dropwise over a period of 90 minutes, with the rate controlled to allow the temperature to rise and be maintained at approximately 80°C by exothermic reaction. After the addition was complete, heat was gently applied to adjust the temperature to 90°C. The mixture was held at 90°C for 60 minutes. A sample was taken, and the mixture was held at 90°C for an additional 30 minutes while an IR spectrum was acquired. No residual isocyanate was detected, and charge 6 was added; the mixture was stirred at 90°C for 30 minutes. Preparation of cationic resin G Table 7A μλ / t / zuzz / uzo ι yy Charge No. Material Quantity (g) 1 Bisphenol A1 diglycidyl ether 614.68 2 Bisphenol A 265.42 3 MACOL 98 A MOD 12 125.0 4 Methyl isobutyl ketone (MIBK) 20.5 5 Ethyltriphenylphosphonium iodide 0.60 6 MACOL 98 A MOD 12 125.0 7 Methyl isobutyl ketone (MIBK) 85.5 8 Blocked polyisocyanate curing agent F (see Table 6 above) 718.4 9 Cetimine3 57.01 10 N-Methylethanolamine 48.68 Spent resin from reaction product of materials 1-10 1854.8 11 Sulfamic acid 40.52 12 Deionized water 1193.2 13 Rosin solution rubber4 16.5 14 Deionized water 690.0 15 Deionized water 223.3 16 Deionized water 1100.0 1Epoxy resin available through Hexion Specialty Chemicals as EPON 828. 2Bisphenol ethylene oxide adduct available through BASF Corporation. 3Dicetimine of MIBK from diethylenetriamine at 72.7% in MIBK. 4. Gum rosin solution 30% by weight in diethylene glycol formal monobutyl ether.

[0192] Charges 1, 2, 3, 4, and 5 were loaded into a four-necked round-bottom flask fitted with a stirrer and a temperature measuring probe, and covered with nitrogen. The mixture was heated to 130°C and allowed to undergo exothermic reaction to approximately 150°C. The temperature was then allowed to drop to 145°C, and the mixture was held at this temperature for 2 hours. Charge 6 was added while the mixture was allowed to cool to 125°C, and then charge 7 was added. Charges 8, 9, and 10 were added, and the mixture was held at 122°C for two hours. 1,854.8 g of this resin were poured into a mixture of 1,193.2 g of deionized water, 40.52 g of sulfamic acid, and 16.5 g of gum rosin solution at room temperature and mixed for 45 minutes. Then, charge 14 was added with stirring for about 30 minutes. Charge 15 was added and mixed for about 30 more minutes. Charge 16 was added and mixed for approximately 15 minutes.Then, about 1,100 g of water and solvent were vacuum distilled with heat at approximately 60-65°C. The final aqueous dispersion had a measured solids content of 42.5%, as determined using the method described in Example 1. Preparation of the electrodepositable coating composition Table 7B μλ / iyy Charge No. Material Example of ABC Electrodepositable Coating Composition 1 Cationic Resin G 1437.2 1406.6 1398.6 2 Cationic Resin E 170.5 170.5 170.5 3 Butylcarbitol formal2 7.0 7.0 7.0 4 Methoxypropanol 9.7 9.7 9.7 5 Acrylic Polymer A 0.0 62.3 124.5 6 Pigment Paste3 339.7 339.7 339.7 7 Water DI 1836.0 1804.3 1750.1 1Described in US8884059B2, example 11. 2Available as Amazon 1651 through BASF Corporation. 3E6436Z pigment paste available through PPG Industries, Inc.

[0193] For each paint composition, charges 1-5 were added sequentially to a plastic container at room temperature with stirring, with 10 minutes of stirring after each addition. The mixture was stirred for at least 30 minutes at room temperature. Charge 6 was then added, and the paint was stirred until uniform, for a minimum of 30 minutes. Charge 7 was added, and the paint was stirred until uniform for a minimum of 30 minutes. The resulting cationic electrodepositable paint compositions had a solids content of 23.0% by weight, determined as described above, and a pigment-to-binder ratio of 0.15 / 1.0 by weight.

[0194] After 25% ultrafiltration (and reconstitution with deionized water), the coated panels were prepared from baths containing the cationic electrodepositable paint compositions separately and were evaluated for oil stain resistance. The results are reported below. Evaluation of the composition of electrodepositable coating of Examples A - C - Drill bit edge coverage

[0195] To evaluate edge corrosion, test panels were specially prepared from 4 x 12 x 0.031-inch cold-rolled steel panels pretreated with CFIEMFOS C700 / DI and available through ACT Laboratories of Hillside, Michigan. The 4 x 12 x 0.31-inch panels were first cut into two 4 x 5-3 / 4-inch panels using a Di-Acro No. 24 hand shear (DiAcro, Oak Park Heights, Minnesota). The panels are positioned in the shear so that the drill bit edge of the cut along the 4-inch edge ends on the opposite side of the top surface of the panel. Next, each 4 x 5-3 / 4 panel is positioned in the cutter to remove 1 inch from one of the 5-3 / 4 inch sides of the panel so that the resulting drill bit from the cut faces upward from the top surface of the panel.

[0196] The electrodepositable paint compositions described above were then electrodeposited onto these specially prepared panels in a manner well known in the art, by immersing them in a stirring bath at 30°C and connecting the cathode of the DC rectifier to the panel and the anode of the DC rectifier to the stainless steel tube used to circulate the cooling water for temperature control of the bath. The voltage was increased from 0 to a setpoint voltage of 150–170 V over a period of 30 seconds and then held at that voltage for an additional 20–120 seconds to achieve the desired film thickness. This combination of time, temperature, and voltage deposited a coating that, when cured, had a dry film thickness of 17 micrometers. Three panels were electroplated for each paint composition.After electrodeposition, the panels were removed from the bath, vigorously rinsed with a spray of deionized water and cured by baking for 25 minutes at 178°C in an electric oven.

[0197] These cured panels were then placed in a salt spray cabinet such that the drill bit along the 5-3 / 4 inch side of the panel was horizontal and the top edge of the drill bit faced outward toward the sprayer. Consequently, the drill bit along the 3-3 / 4 inch side of the panel was vertical and the edge of the drill bit faced backward. These panels were subjected to salt spray exposure for a period of three days, so that all areas along the 5-3 / 4 inch (145 mm) of the drill bit that were not well protected by the electrocoating would oxidize. The salt spray test is the same as that used to evaluate blades and is described in detail in ASTM BI 17. After exposure to salt spray, the length of the drill bit that remained well protected by the electrocoating was measured (coated edge + oxidized edge = 145 mm).Due to panel-to-panel variation, the drill bit length of each of the three panels was evaluated. The percentage of remaining coating along the drill bit length was then calculated. Finally, the average percentage coverage of the three drill bit lengths for the three individual panels was taken. As shown in the table below, these averages demonstrated that the differences due to varying paint compositions were significantly greater than the differences between panels for a given paint composition. This test method is referred to herein as the drill bit edge coverage test method.

[0198] The coated panels were also evaluated for gloss. The 20° and 60° gloss were measured using a BYK Gardner turbidity meter (catalog no. 4601) in accordance with ASTM D523. ma / iyy Table 8 Coating Composition Example of Acrylic Polymer Amount of Acrylic Polymer (% of Total Resin Solids) Panel I No. mm of Coverage (145 mm Edge) % of Remaining Coverage Average % of Edge Coverage Gloss -20° Gloss -60° A None 0% 1 1 0.69 0.2 23 68 2 0 0.00 3 0 0.00 BA 0.5% 1 78 53.79 37.2 7 38 2 40 27.59 3 44 30.34 CA 1.0% 1 96 66.21 45.5 5 30 2 70 48.28 3 32 22.07

[0199] The results in Table 8 demonstrate that the inclusion of the acrylic polymer of the present invention in an electrodepositable coating composition results in improved corrosion resistance of a substrate coated with the electrodepositable coating composition. For example, the experimental coating compositions B and C showed significantly improved coverage on the substrate after the salt spray corrosion test compared to the comparator coating composition A, which did not include the acrylic polymer.

[0200] The results in Table 8 also demonstrated significantly improved gloss performance for coating compositions B and C relative to the comparator coating composition A that did not include the acrylic polymer.

[0201] Persons of the middle trade will appreciate that numerous modifications and variations are possible in light of the foregoing disclosure without departing from the broad inventive concepts described and exemplified herein. Accordingly, therefore, the foregoing disclosure should be understood as merely illustrative of various exemplary aspects of this application, and that persons of the middle trade may readily make numerous modifications and variations within the spirit and scope of this application and the accompanying claims.

Claims

1. An electrodepositable coating composition comprising: (a) an acrylic polymer comprising more than 60% by weight of constitutional units comprising the residue of a hydroxyl-functional (meth)acrylate monomer and / or a hydroxyl-functional (meth)acrylamide monomer, based on the total weight of the acrylic polymer; and (b) a film-forming polymer containing an ionic salt group different from the acrylic polymer.

2. The electrodepositable coating composition according to claim 1, wherein the acrylic polymer comprises a linear polymer, a branched polymer and / or a crosslinked polymer network.

3. The electrodepositable coating composition according to claim 1, wherein the hydroxyl-functional (meth)acrylate monomer comprises a Ci-Cio hydroxyalkyl (meth)acrylate.

4. The electrodepositable coating composition according to claim 1, wherein the hydroxyl-functional (meth)acrylate monomer comprises hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, or a combination thereof.

5. The electrodepositable coating composition according to claim 1, wherein the hydroxyl-functional (meth)acrylate monomer and / or the hydroxyl-functional (meth)acrylamide monomer comprises a hydroxyl group.

6. The electrodepositable coating composition according to claim 1, wherein the acrylic polymer further comprises constitutional units comprising the residue of an unsaturated monomer that does not contain hydroxyl.

7. The electrodepositable coating composition according to claim 1, wherein the acrylic polymer comprises 70% to 100% by weight of constitutional units comprising the residue of the hydroxyl-functional (meth)acrylate monomer, wherein the % by weight is a function of the total weight of the acrylic polymer.

8. The electrodepositable coating composition according to claim 1, wherein the acrylic polymer has a theoretical hydroxyl equivalent weight of 100 g / OH to 500 g / OH.

9. The electrodepositable coating composition according to claim 1, wherein the acrylic polymer has an average molecular weight at z of 500,000 g / mol to 60,000,000 g / mol, as determined by gel permeation chromatography using polystyrene calibration standards.

10. The electrodepositable coating composition according to claim 1, wherein the acrylic polymer comprises a single-stage acrylic polymer.

11. The electrodepositable coating composition according to claim 1, wherein the acrylic polymer is substantially silicon-free.

12. The electrodepositable coating composition according to claim 1, wherein the acrylic polymer is substantially free of constitutional units comprising nitrogen-containing monomer residue.

13. The electrodepositable coating composition according to claim 1, wherein the acrylic polymer is substantially free of constitutional units comprising diene monomer residue.

14. The electrodepositable coating composition according to claim 1, wherein the acrylic polymer is substantially free of the constitutional units comprising the residue of monomers comprising three or more ethylenically unsaturated groups per molecule.

15. The electrodepositable coating composition according to claim 1, wherein the acrylic polymer is substantially free of constitutional units comprising the isobutylene monomer residue.

16. The electrodepositable coating composition according to claim 1, wherein the film-forming polymer containing an ionic salt group comprises a film-forming polymer containing a cationic salt group.

17. The electrodepositable coating composition according to claim 1, wherein the film-forming polymer containing an ionic salt group comprises a film-forming polymer containing an anionic salt group.

18. The electrodepositable coating composition according to claim 1, further comprising a polyalkylene oxide polymer.

19. The electrodepositable coating composition according to claim 1, further comprising (c) a curing agent.

20. The electrodepositable coating composition according to claim 19, wherein (a) the acrylic polymer is present in an amount of 0.05% to 10% by weight; (b) the film-forming polymer containing an ionic salt group is present in an amount of 40% to 90% by weight; and (c) the curing agent is present in an amount of 10% to 59.95% by weight, wherein the % by weight is a function of the total weight of the resin solids of the electrodepositable coating composition.

21. The electrodepositable coating composition according to claim 1, wherein the electrodepositable coating composition is substantially free of silicon dioxide microspheres and silicon dioxide nanospheres.

22. A method for coating a substrate comprising electrophoretically applying a coating deposited from the electrodepositable coating composition according to claim 1 onto at least a portion of the substrate.

23. A substrate comprising a coating deposited from the electrodepositable coating composition according to claim 1 onto at least a portion of the substrate.

24. The substrate according to claim 23, wherein the coating has a gloss value reduction of at least 20% when the acrylic polymer is present in the electrodepositable coating composition in an amount of 0.5% by weight based on the total resin solids, wherein the gloss value is measured according to ASTM D523 and the gloss value reduction is compared to a substrate coated with a comparative electrodepositable coating composition that does not include the acrylic polymer but otherwise has the same composition as the electrodepositable coating composition.

25. The substrate according to claim 23, wherein the coating has a 60° gloss value reduction of at least 20%, when the acrylic polymer is present in the electrodepositable coating composition in an amount of 0.5% by weight based on the total resin solids, the gloss values ​​measured according to ASTM D523, and the gloss value reduction compared to a substrate coated with a comparative electrodepositable coating composition that does not include the acrylic polymer but otherwise has the same composition as the electrodepositable coating composition.

26. The substrate according to claim 23, wherein the average edge coverage percentage of the coated substrate is improved by at least 20%, as measured according to the drill edge coverage test method, compared to a substrate coated with a comparative electrodepositable coating composition that does not include the acrylic polymer but otherwise has the same composition as the electrodepositable coating composition.