Electrodepositable coating composition

Abstract

The present disclosure relates to an electrodepositable coating composition comprising (a) an active hydrogen-containing ionic base-containing film-forming polymer; (b) at least partially blocked polyisocyanate curing agent; (c) a curing catalyst; and (d) an edge control adduct, wherein the electrodepositable coating composition has a gel point of less than 150°C as measured by a gel point test method, an edge coverage greater than 20% as measured by an edge coverage test method, and an Ra of 0.45 or less as measured by a surface roughness test method. Additionally, a method for coating a substrate, the coating, and the coated substrate are disclosed.

Description

Technology Field

[0001] This application claims priority and benefit of U.S. Provisional Application No. 63 / 217,547 filed July 1, 2021, U.S. Provisional Application No. 63 / 217,517 filed July 1, 2021, and U.S. Provisional Application No. 63 / 253,344 filed October 7, 2021, which are respectively incorporated herein by reference.

[0002] The present disclosure relates to an electrodepositable coating composition, a coated substrate, and a method for coating a substrate. Background Technology

[0003] Electrodeposition as a coating application method involves depositing a film-forming composition onto a conductive substrate under the influence of an applied potential. Electrodeposition is gaining popularity in the coating industry because it offers high paint utilization, excellent corrosion resistance, and low environmental pollution compared to non-electrophoretic coating methods. Both cationic and anionic electrodeposition processes are commercially utilized.

[0004] The present disclosure provides an electrodepositable coating composition, comprising (a) an active hydrogen-containing ionic base-containing film-forming polymer; (b) blocked polyisocyanate curing agent; (c) curing catalyst; and (d) edge control additive, wherein the electrodepositable coating composition has a gel point less than 150°C, less than 145°C, less than 140°C, less than 135°C, less than 130°C, or less than 125°C as measured by the gel point test method, an edge coverage greater than 20% as measured by the edge coverage test method, and an Ra less than 0.45 as measured by the surface roughness test method.

[0005] Additionally, the present disclosure provides an electrodepositable coating composition comprising (a) an active hydrogen-containing ionic base-containing film-forming polymer comprising (1) a polyepoxide; (2) a difunctional chain extender; and (3) a reaction product of a reaction mixture comprising a monofunctional reactant; (b) a blocked polyisocyanate curing agent; (c) a curing catalyst; and (d) an edge control adduct, wherein the electrodepositable coating composition has a gelation point of less than 150°C, less than 145°C, less than 140°C, less than 135°C, less than 130°C, or less than 125°C as measured by a gelation point test method, and a bonding temperature of less than 90°F as measured by a bonding temperature test method.

[0006] Additionally, the present disclosure further provides a method for coating a substrate, comprising the step of electrophoretically applying a coating deposited from the electrodepositable coating composition of the present disclosure to at least a portion of the substrate.

[0007] In addition, the present disclosure provides at least partially cured coating formed by at least partially curing a coating deposited from the electrodepositable coating composition of the present disclosure.

[0008] In addition, the present disclosure relates to a coated substrate comprising a coating formed by electrodepositing the electrodepositable coating composition of the present disclosure onto a substrate and curing the coating at least partially. Specific details for implementing the invention

[0009] The present disclosure relates to an electrodepositable coating composition, comprising (a) an active hydrogen-containing ionic base-containing film-forming polymer; (b) a polyisocyanate curing agent that is at least partially blocked; (c) a curing catalyst; and (d) an edge control adduct, wherein the electrodepositable coating composition has a gelation point of less than 150°C as measured by the gelation point test method, an edge coverage of more than 20% as measured by the edge coverage test method, and an Ra of 0.45 or less as measured by the surface roughness test method.

[0010] The present disclosure relates to an electrodepositable coating composition comprising: (a) an active hydrogen-containing ionic base-containing film-forming polymer comprising a reaction product of a reaction mixture comprising (1) a polyepoxide; (2) a difunctional chain extender; and (3) a monofunctional reactant; (b) a blocked polyisocyanate curing agent; (c) a curing catalyst; and (d) an edge control adduct, wherein the electrodepositable coating composition has a gelation point of less than 150°C, less than 145°C, less than 140°C, less than 135°C, less than 130°C, or less than 125°C as measured by a gelation point test method, and a bonding temperature of less than 90°F as measured by a bonding temperature test method.

[0011] The term "electrodepositable coating composition" refers to a composition that can be deposited on an electrically conductive substrate under the influence of an applied potential.

[0012] The electrodeposited coating composition has a gelation point of less than 150°C as measured by the gelation point test method. The electrodeposited coating composition may have a gelation point of less than 145°C, e.g., less than 140°C, e.g., less than 135°C, e.g., less than 130°C, e.g., less than 125°C as measured by the gelation point test method.

[0013] The "gelling point test method" used herein refers to a test method of coating a target electrodepositable coating composition onto a test panel until it reaches a target film of 0.7 to 0.9 mils (17 to 23 microns). Subsequently, the applied uncured coating is dissolved in THF, deposited on a platen, placed on a durometer at a constant shear strain and frequency, the temperature is increased from 40°C to 175°C at a rate of 3.3°C / min, and the complex viscosity (cps, η*), shear strain (%, γ), loss factor (G” / G'), loss modulus (Pa, G”), storage modulus (Pa, G'), and shear stress (Pa, τ) are measured over the temperature gradient, and the gelation point is determined as the point where the loss modulus (G”) intersects the storage modulus (G'). The specific method for the gelation point test is as follows: The electrodepositable coating composition is coated on a 4" X 12" .025" panel. Subsequently, the applied uncured coating is dissolved in THF and deposited on a type P-PTD200 / 56 platen and placed on an Anton Paar hardness tester (model 302) using an Anton Paar PPR 25 / 23 spindle and a setting of constant 5% shear strain and constant 1 Hz frequency. The temperature is maintained at 40°C for 30 minutes and then increased from 40°C to 175°C at a rate of 3.3°C / min. Complex viscosity (cps, η*), shear strain (%, γ), loss modulus (G” / G'), loss modulus (Pa, G”), storage modulus (Pa, G'), and shear stress (Pa, τ) are measured over the temperature gradient, and the gelation point is determined as the point where the loss modulus (G”) intersects the storage modulus (G').

[0014] The electrodeposited coating composition has an edge coverage of more than 20% as measured by the edge coverage test method. The electrodeposited coating composition may have an edge coverage of more than 25%, e.g., more than 30%, e.g., more than 35%, e.g., more than 40%, e.g., more than 45%, e.g., more than 50%, e.g., more than 55%, e.g., more than 60%, e.g., more than 65%, e.g., more than 70%, e.g., more than 75% as measured by the edge coverage test method.

[0015] The “edge coverage test method” used herein is performed as follows: The test panel is specially manufactured from a cold-rolled steel panel, 4 x 12 x 0.032 inch, pretreated with CHEMFOS C700 / DI and available from ACT Laboratories, Hillsdale, Michigan. First, a 4 x 12 x 0.31 inch panel was cut into two 4 x 5-3 / 4 inch panels using Di-Acro Hand Shear No. 24 (DiAcro, Oak Park Heights, Minnesota). The panel was positioned on the cutter so that the bur edge from the cut along the 4-inch edge stopped on the side facing the top surface of the panel. Subsequently, each 4 × 5-3 / 4 panel was positioned on the cutter to remove ¼ inch from one of the 5-3 / 4-inch sides of the panel in such a way that the bur obtained from the cut faced upward toward the top surface of the panel. Subsequently, the electrodepositable coating composition is electrodeposited onto these specially manufactured panels. The coated panels are cured by methods such as firing in an electric oven (Despatch Industries, model LFD series) at 150°C for 20 minutes. After firing at 150°C for 20 minutes, each panel has a dry film thickness of 0.7 to 0.9 mils (17 to 23 microns).

[0016] Using a Di-Acro panel cutter (model number 12 SHEAR), cut a square piece approximately 0.5 inches x 0.5 inches from the burr edge of the panel. Then, secure the panel piece inside a Leco mold cup using Ted Pella plastic multi-clips. Mix Leco epoxy (811-563-101) and Leco hardener (812-518) in a 100:14 ratio, pour into the mounting cup containing the burr specimen, and cure overnight at room temperature. Subsequently, grind and polish the epoxy mount using a Leco Spectrum System 1000 grinder / grinder with Leco grit paper according to the following process: 240 grit (2 times per minute), 320 grit (1 or 2 times per minute), 600 grit (2 times per 30 seconds), and 1200 grit (2 times per 30 seconds). Subsequently, the specimen is polished for 2 minutes using 1-micron diamond paste or 1200 grit sandpaper. The grinding / polishing process may vary slightly depending on the appearance of the epoxy mount surface. Once polished, the specimen was coated with Au / Pd for 20 seconds using an EMS150T ES sputter coater and placed on an aluminum mount with carbon tape. The specimen was then imaged using an FEI Quanta FEG 250 SEM at 10 kV. Measurements of the film formed on the burr are captured. Three measurements are taken from the tip of the burr and averaged. Three film formation measurements are captured from the flat (burr-free) portion of the specimen and averaged. The edge coverage percentage is determined by calculating the ratio of the film formed on the burr and the flat portion of the specimen.

[0017] The electrodeposited coating composition has an Ra of 0.45 or less as measured by a surface roughness test method. The electrodeposited coating composition may have an Ra of 0.40 or less, e.g., 0.35 or less, e.g., 0.31 or less, e.g., 0.25 or less, e.g., 0.20 or less, e.g., 0.15 as measured by a surface roughness test method.

[0018] The "surface roughness test method" used herein refers to a test method in which an electrodepositable coating composition is electrodeposited onto a metal panel and cured, the coating texture is evaluated using a profilometer over a specified length of the panel, and the roughness profile is filtered according to ISO 4287-1997 3.1.6 using an Lc parameter of 2.5 mm and an Ls parameter of 8 μm before summarizing the Ra measurement parameter (hereinafter referred to as Ra) according to ISO 4287-1997 4.2.1. A specific test procedure may be performed as follows: The electrodepositable coating composition may be electrodeposited onto a metal panel measuring 4x6x0.032 inches and the coating may be cured by firing it in an electric oven. The coating texture may be evaluated using a Mitutoyo Surftest SJ-402 skid dress stylus profilometer equipped with a 4 mN detector and a diamond stylus tip having a 90° cone and a 5 μm tip radius. The scan length, measurement speed, and data sampling interval can be 48 mm, 1 mm / s, and 5 μm, respectively. First, the raw data can be filtered into a roughness profile according to ISO 4287-1997 3.1.6 using an Lc parameter of 2.5 mm and an Ls parameter of 8 μm before summarizing the Ra measurement item according to ISO 4287-1997 4.2.1.

[0019] The "adhesion temperature test method" used herein involves an electrodepositable coating composition using a voltage of 190 V and a deposition time of 3 minutes. 70 to 3℉ bathtub temperature intervals This refers to a test method in which electrodeposition is performed on a 4 x 6 x 0.031 inch test panel at an electrodeposition bath temperature of 102℉ (maximum 102℉). Film formation is measured using a Fischer Dualscope FMP40 permascope instrument. If a minimum film formation value is identified within the tested temperature range, the temperature at which the lowest film formation is measured is referred to as the adhesion temperature.

[0020] The electrodeposited coating composition may have a smoothness % of at least 30%, e.g., at least 35%, e.g., at least 40%, e.g., at least 45%, e.g., at least 50%, e.g., at least 55%, e.g., at least 60%, e.g., at least 65%, e.g., at least 70%, e.g., at least 75%, e.g., at least 80% as measured by a smoothness test method. "Smoothness %" as used herein refers to a reduction in panel surface roughness after the electrodeposited coating composition is applied to the surface of a substrate and fired. For example, a substrate in which Ra is 0.6 before electrocoating and Ra is 0.3 after the application of the electrodeposited coating composition means that the electrodeposited coating composition has a smoothness % of 50%. Likewise, a substrate with an Ra of 0.6 before electrocoating and an Ra of 0.15 after the application of the electrodeposited coating composition means that the electrodeposited coating composition has a smoothness % of 75%.

[0021] The "smoothness test method" used herein refers to a test method for evaluating panel texture before and after electrocoating. First, panel roughness is evaluated using a profilometer at specified scan lengths, measurement speeds, and data sampling intervals, respectively. First, raw sampling data is filtered into a roughness profile according to ISO 4287-1997 3.1.6 using Lc parameters of 2.5 mm and Ls parameters of 8 μm, before summarizing the Ra measurement parameter (hereinafter referred to as Ra) according to ISO 4287-1997 4.2.1. Subsequently, the panel is electrocoated using an electrodepositable coating composition. Subsequently, the coated substrate is evaluated in the same manner as the uncoated substrate. The smoothness % is calculated as 1 - (Ra of the coated panel / Ra of the previous panel) x 100.

[0022] Film-forming polymers containing active hydrogen and ionic bases

[0023] The electrodepositable coating composition further comprises an active hydrogen-containing ionic base-containing film-forming polymer. The ionic base-containing film-forming polymer may include a cationic base-containing film-forming polymer or an anionic base-containing film-forming polymer.

[0024] The ionic base-containing film-forming polymer may optionally comprise a reaction product of a reaction mixture comprising (a) a polyepoxide; (b) a difunctional chain extender; and (c) a monofunctional reactant.

[0025] The polyepoxide may include any suitable polyepoxide. For example, the polyepoxide may include a diepoxide. Non-limiting examples of suitable polyepoxide include diglycidyl ethers of bisphenol, such as diglycidyl ethers of bisphenol A or bisphenol F.

[0026] The difunctional chain extender may include any suitable difunctional chain extender. For example, the difunctional chain extender may include a dihydroxyl functional reactant, a dicarboxylic acid functional reactant, or a primary amine functional reactant. The dihydroxyl functional reactant may include, for example, bisphenol, e.g., bisphenol A and / or bisphenol F. The dicarboxylic acid functional reactant may include, for example, dimeric fatty acids.

[0027] The monofunctional reactant may include monophenol, monofunctional acid, dimethylethanolamine, monoepoxide, e.g., glycidyl ether of phenol, glycidyl ether of nonylphenol, or glycidyl ether of cresol, or any combination thereof.

[0028] Monophenol may include any suitable monophenol. For example, monophenol may include phenol, 2-hydroxytoluene, 3-hydroxytoluene, 4-hydroxytoluene, 2-tertiary-butylphenol, quaternary-butylphenol, 2-tertiary-butyl-4-methylphenol, 2-methoxyphenol, 4-methoxyphenol, 2-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, nonylphenol, dodecylphenol, 1-hydroxynaphthalene, 2-hydroxynaphthalene, biphenyl-2-ol, biphenyl-4-ol, and 2-allylphenol.

[0029] The monofunctional acid may include any compound or mixture of compounds having one carboxyl group per molecule. In addition to the carboxyl group, the monofunctional acid may include other functional groups that do not chemically react with the epoxide, hydroxyl, or carboxyl functional groups and thus do not interfere with the polymerization reaction. The monofunctional acid may include aromatic mono acids, e.g., benzoic acid or phenylalkaline acids, e.g., phenylacetic acid, 3-phenylpropaneic acid, etc., and aliphatic mono acids and combinations thereof.

[0030] The ratio of the functional groups of the difunctional chain extender and monofunctional reactant to the epoxide functional groups of the polyepoxide may be at least 0.50:1, e.g., at least 0.60:1, e.g., at least 0.65:1, e.g., at least 0.70:1. The ratio of the functional groups of the difunctional chain extender and monofunctional reactant to the epoxide functional groups of the polyepoxide may be 0.85:1 or less, e.g., 0.80:1 or less, e.g., 0.75:1 or less, e.g., 0.70:1 or less. The ratio of the functional groups of the difunctional chain extender and monofunctional reactant to the epoxide functional groups of the polyepoxide is 0.50:1 to 0.85:1, e.g., 0.50:1 to 0.80:1, e.g., 0.50:1 to 0.75:1, e.g., 0.50:1 to 0.70:1, e.g., 0.60:1 to 0.85:1, e.g., 0.60:1 to 0.80:1, e.g., 0.60:1 to 0.75:1, e.g., 0.60:1 to 0.70:1, e.g., 0.65:1 to 0.85:1, e.g., 0.65:1 to 0.80:1, e.g., 0.65:1 to 0.75:1, e.g., 0.65:1 to 0.70:1, e.g., It may be 0.70:1 to 0.85:1, for example, 0.70:1 to 0.80:1, for example, 0.70:1 to 0.75:1.

[0031] The difunctional chain extender may include a di-hydroxyl functional reactant, e.g., bisphenol. The ratio of the total phenolic hydroxyl groups of the bisphenol difunctional chain extender and the functional groups of the monofunctional reactant to the epoxide functional groups of the polyepoxide may be at least 0.50:1, e.g., at least 0.60:1, e.g., at least 0.65:1, e.g., at least 0.70:1. The ratio of the total phenolic hydroxyl groups of the bisphenol difunctional chain extender and the functional groups of the monofunctional reactant to the epoxide functional groups of the polyepoxide may be 0.85:1 or less, e.g., 0.80:1 or less, e.g., 0.75:1 or less, e.g., 0.70:1 or less. The ratio of the phenolic hydroxyl groups of the total bisphenol difunctional chain extender and the functional groups of the monofunctional reactant to the epoxide functional groups of the polyepoxide is 0.50:1 to 0.85:1, e.g., 0.50:1 to 0.80:1, e.g., 0.50:1 to 0.75:1, e.g., 0.50:1 to 0.70:1, e.g., 0.60:1 to 0.85:1, e.g., 0.60:1 to 0.80:1, e.g., 0.60:1 to 0.75:1, e.g., 0.60:1 to 0.70:1, e.g., 0.65:1 to 0.85:1, e.g., 0.65:1 to 0.80:1, e.g., 0.65:1 to 0.75:1, e.g., 0.65:1 to It may be 0.70:1, for example, 0.70:1 to 0.85:1, for example, 0.70:1 to 0.80:1, for example, 0.70:1 to 0.75:1.

[0032] The difunctional chain extender may include a dihydroxyl functional reactant, e.g., bisphenol. The ratio of the phenolic hydroxyl group of the total bisphenol difunctional chain extender and the acid group of the monofunctional acid to the epoxide functional group of the polyepoxide may be at least 0.50:1, e.g., at least 0.60:1, e.g., at least 0.65:1, e.g., at least 0.70:1. The ratio of the phenolic hydroxyl group of the total bisphenol difunctional chain extender and the acid group of the monofunctional acid to the epoxide functional group of the polyepoxide may be 0.85:1 or less, e.g., 0.80:1 or less, e.g., 0.75:1 or less, e.g., 0.70:1 or less. The ratio of the phenolic hydroxyl groups of the total bisphenol difunctional chain extender and the acid groups of the monofunctional acid to the epoxide functional groups of the polyepoxide is 0.50:1 to 0.85:1, e.g., 0.50:1 to 0.80:1, e.g., 0.50:1 to 0.75:1, e.g., 0.50:1 to 0.70:1, e.g., 0.60:1 to 0.85:1, e.g., 0.60:1 to 0.80:1, e.g., 0.60:1 to 0.75:1, e.g., 0.60:1 to 0.70:1, e.g., 0.65:1 to 0.85:1, e.g., 0.65:1 to 0.80:1, e.g., 0.65:1 to 0.75:1, e.g., 0.65:1 to It may be 0.70:1, for example, 0.70:1 to 0.85:1, for example, 0.70:1 to 0.80:1, for example, 0.70:1 to 0.75:1.

[0033] The difunctional chain extender may include a di-hydroxyl functional reactant, e.g., bisphenol. The ratio of the phenolic hydroxyl group of the total bisphenol difunctional chain extender to the phenolic hydroxyl group of monophenol to the epoxide functional group of polyepoxide may be at least 0.50:1, e.g., at least 0.60:1, e.g., at least 0.65:1, e.g., at least 0.70:1. The ratio of the phenolic hydroxyl group of the total bisphenol difunctional chain extender to the phenolic hydroxyl group of monophenol to the epoxide functional group of polyepoxide may be 0.85:1 or less, e.g., 0.80:1 or less, e.g., 0.75:1 or less, e.g., 0.70:1 or less. The ratio of the phenolic hydroxyl groups of the total bisphenol difunctional chain extender and the phenolic hydroxyl groups of the monophenol to the epoxide functional groups of the polyepoxide is 0.50:1 to 0.85:1, e.g., 0.50:1 to 0.80:1, e.g., 0.50:1 to 0.75:1, e.g., 0.50:1 to 0.70:1, e.g., 0.60:1 to 0.85:1, e.g., 0.60:1 to 0.80:1, e.g., 0.60:1 to 0.75:1, e.g., 0.60:1 to 0.70:1, e.g., 0.65:1 to 0.85:1, e.g., 0.65:1 to 0.80:1, e.g., 0.65:1 to 0.75:1, e.g., It may be 0.65:1 to 0.70:1, for example, 0.70:1 to 0.85:1, for example, 0.70:1 to 0.80:1, for example, 0.70:1 to 0.75:1.

[0034] The difunctional chain extender may include a dihydroxyl functional reactant, e.g., bisphenol. The ratio of the phenolic hydroxyl functional group of the bisphenol difunctional chain extender to the phenolic hydroxyl functional group of monophenol and / or the acid group of the monofunctional acid may be at least 0.05:1, e.g., at least 0.1:1, e.g., at least 0.2:1, e.g., at least 0.3:1, e.g., at least 0.4:1, e.g., at least 0.5:1, e.g., at least 0.6:1, e.g., at least 0.7:1, e.g., at least 0.8:1. The ratio of the phenolic hydroxyl functional group of the bisphenol difunctional chain extender to the phenolic hydroxyl functional group of monophenol may be 9:1 or less, e.g., 4:1 or less, e.g., 2:1 or less, e.g., 1:1 or less, e.g., 0.8:1 or less. The ratio of the phenolic hydroxyl functional group of the bisphenol difunctional chain extender to the phenolic hydroxyl functional group of the monophenol is 0.05:1 to 9:1, e.g., 0.05:1 to 4:1, e.g., 0.05:1 to 2:1, e.g., 0.05:1 to 1:1, e.g., 0.05:1 to 0.8:1, e.g., 0.1:1 to 9:1, e.g., 0.1:1 to 4:1, e.g., 0.1:1 to 2:1, e.g., 0.1:1 to 1:1, e.g., 0.1:1 to 0.8:1, e.g., 0.2:1 to 9:1, e.g., 0.2:1 to 4:1, e.g., 0.2:1 to 2:1, e.g., 0.2:1 to 1:1, e.g., 0.2:1 to 0.8:1, e.g., 0.3:1 to 9:1, e.g., 0.3:1 to 4:1, e.g., 0.3:1 to 2:1, e.g., 0.3:1 to 1:1, e.g., 0.3:1 to 0.8:1, e.g., 0.4:1 to 9:1, e.g., 0.4:1 to 4:1, e.g., 0.4:1 to 2:1, e.g., 0.4:1 to 1:1, e.g., 0.4:1 to 0.8:1, e.g., 0.5:1 to 9:1, e.g., 0.5:1 to 4:1, e.g., 0.It may be 5:1 to 2:1, for example, 0.5:1 to 1:1, for example, 0.5:1 to 0.8:1, for example, 0.6:1 to 9:1, for example, 0.6:1 to 4:1, for example, 0.6:1 to 2:1, for example, 0.6:1 to 1:1, for example, 0.6:1 to 0.8:1, for example, 0.7:1 to 9:1, for example, 0.7:1 to 4:1, for example, 0.7:1 to 2:1, for example, 0.7:1 to 1:1, for example, 0.7:1 to 0.8:1, for example, 0.8:1 to 9:1, for example, 0.8:1 to 4:1, for example, 0.8:1 to 2:1, for example, 0.8:1 to 1:1.

[0035] The reaction product of a reaction mixture comprising (a) polyepoxide; (b) a difunctional chain extender; and (c) a monofunctional reactant may have an epoxy equivalent of at least 700 g / equivalent, e.g., at least 800 g / equivalent, e.g., at least 850 g / equivalent. The reaction product of a reaction mixture comprising (a) polyepoxide; (b) a difunctional chain extender; and (c) a monofunctional reactant may have an epoxy equivalent of 1,500 g / equivalent or less, e.g., 1,400 g / equivalent or less, e.g., 1,200 g / equivalent or less, e.g., 1,100 g / equivalent or less. (a) polyepoxide; (b) a difunctional chain extender; and (c) the reaction product of the reaction mixture comprising a monofunctional reactant may have an epoxy equivalent of 700 to 1,500 g / equivalent, e.g., 700 to 1,400 g / equivalent, e.g., 700 to 1,200 g / equivalent, e.g., 700 to 1,100 g / equivalent, e.g., 800 to 1,500 g / equivalent, e.g., 800 to 1,400 g / equivalent, e.g., 800 to 1,200 g / equivalent, e.g., 800 to 1,100 g / equivalent, e.g., 850 to 1,500 g / equivalent, e.g., 850 to 1,400 g / equivalent, e.g., 850 to 1,200 g / equivalent, e.g., 850 to 1,100 g / equivalent.

[0036] The reaction product of a reaction mixture comprising (a) a polyepoxide; (b) a difunctional chain extender; and (c) a monofunctional reactant has a z-average molecular weight (M) as determined by gel permeation chromatography using a polystyrene calibration standard. z) may be at least 8,000 g / mol, e.g., at least 10,000 g / mol, e.g., at least 12,000 g / mol, e.g., at least 13,000 g / mol, e.g., at least 15,000 g / mol, e.g., at least 20,000 g / mol. The reaction product of a reaction mixture comprising (a) a polyepoxide; (b) a difunctional chain extender; and (c) a monofunctional reactant has a z-average molecular weight (M) as determined by gel permeation chromatography using a polystyrene calibration standard. z ) may be 35,000 g / mol or less, e.g., 25,000 g / mol or less, e.g., 20,000 g / mol or less, e.g., 15,000 g / mol or less. The reaction product of a reaction mixture comprising (a) a polyepoxide; (b) a difunctional chain extender; and (c) a monofunctional reactant has a z-average molecular weight (M) as determined by gel permeation chromatography using a polystyrene calibration standard. z) is 8,000 g / mol to 35,000 g / mol, e.g., 8,000 g / mol to 25,000 g / mol, e.g., 8,000 g / mol to 20,000 g / mol, e.g., 8,000 to 15,000 g / mol, e.g., 10,000 g / mol to 35,000 g / mol, e.g., 10,000 g / mol to 25,000 g / mol, e.g., 10,000 g / mol to 20,000 g / mol, e.g., 10,000 to 15,000 g / mol, e.g., 12,000 g / mol to 35,000 g / mol, e.g., 12,000 g / mol to 25,000 g / mol, e.g., 12,000 g / mol to It may be 20,000 g / mol, for example, 12,000 to 15,000 g / mol, for example, 13,000 g / mol to 35,000 g / mol, for example, 13,000 g / mol to 25,000 g / mol, for example, 13,000 g / mol to 20,000 g / mol, for example, 13,000 to 15,000 g / mol, for example, 15,000 g / mol to 35,000 g / mol, for example, 15,000 g / mol to 25,000 g / mol, for example, 15,000 g / mol to 20,000 g / mol, for example, 20,000 to 35,000 g / mol, for example, 20,000 g / mol to 25,000 g / mol.

[0037] Unless otherwise stated, the term "z-average molecular weight (M z)" is the z-average molecular weight (M) as determined by gel permeation chromatography using a Waters 2695 separation module equipped with a Waters 410 differential refractometer (RI detector), polystyrene standards having a molecular weight of approximately 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 a single Asahipak GF-510 HQ column for separation. z ) and z-average molecular weight (M z It means ).

[0038] A cationic base may be incorporated into the reaction product of a reaction mixture comprising (a) a polyepoxide; (b) a difunctional chain extender; and (c) a monofunctional reactant as follows: the reaction product may react with a cationic base forming agent. "Cationic base forming agent" means a substance that reacts with an existing epoxy group and can be acidified before, during, or after the reaction with the epoxy group on the reaction product to form a cationic base. Examples of suitable substances include primary or secondary amines that can be acidified after the reaction with the epoxy group to form an amine base group, or amines such as tertiary amines that can be acidified before the reaction with the epoxy group and form a quaternary ammonium salt group after the reaction with the epoxy group. Other examples of cationic base forming agents are sulfides that can be mixed with an acid before the reaction with the epoxy group and can form a ternary sulfonium salt group upon subsequent reaction with the epoxy group.

[0039] An anionic base may be incorporated into the reaction product of a reaction mixture comprising (a) a polyepoxide; (b) a difunctional chain extender; and (c) a monofunctional reactant by reacting the reaction product with a polyprotic acid. Suitable polyprotic acids include, for example, oxyacids of phosphorus such as phosphoric acid and / or phosphonic acid.

[0040] Ionic base-containing film-forming polymers may include cationic base-containing film-forming polymers. Cationic base-containing film-forming polymers may be used in cationic electrodepositable coating compositions. As used herein, the term "cationic base-containing film-forming polymer" refers to a polymer comprising at least partially neutralized cationic functional groups that impart a positive charge, e.g., sulfonium groups and ammonium groups. As used herein, the term "polymer" includes, but is not limited to, both oligomers, homopolymers, and copolymers. Cationic base-containing film-forming polymers may include active hydrogen functional groups. As used herein, the term "active hydrogen functional group" refers to a group reactive with isocyanates as determined by the Zerewitinoff test as discussed above, and includes, e.g., hydroxyl groups, primary or secondary amine groups, and thiol groups. A cationic base-containing film-forming polymer containing an active hydrogen functional group may be referred to as an active hydrogen-containing cationic base-containing film-forming polymer.

[0041] Examples of polymers suitable for use as cationic base-containing film-forming polymers in the present disclosure include, but are not limited to, alkyd polymers, acrylics, polyepoxides, polyamides, polyurethanes, polyureas, polyethers, and polyesters.

[0042] More specific examples of film-forming polymers containing suitable active hydrogen-containing cationic bases include polyepoxide-amine adducts, such as adducts of polyglycidyl ethers of polyphenols such as bisphenol A, and primary and / or secondary amines, which are described, for example, in column 3, line 27 to column 5, line 50 of U.S. Patent No. 4,031,050, column 5, line 58 to column 6, line 66 of U.S. Patent No. 4,452,963, and column 2, line 66 to column 6, line 26 of U.S. Patent No. 6,017,432, parts of which are incorporated herein by reference. Some of the amines reacting with the polyepoxide may be ketimine of the polyamine, which is described in column 6, line 23 to column 7, line 23 of U.S. Patent No. 4,104,147, parts of which are incorporated herein by reference. Additionally, a non-gelled polyepoxide-polyoxyalkylene polyamine resin is suitable, as described in U.S. Patent No. 4,432,850, column 2, lines 60 to column 5, lines 58, the cited portion thereof is incorporated herein by reference. Additionally, cationic acrylic resins, of which portions of both are incorporated herein by reference, such as cationic acrylic resins as described in U.S. Patent No. 3,455,806, column 2, lines 18 to column 3, lines 61 and U.S. Patent No. 3,928,157, column 2, lines 29 to column 3, lines 21, may be used.

[0043] In addition to amine base-containing resins, quaternary ammonium base-containing resins may also be used in the present disclosure as cationic base-containing film-forming polymers. Examples of such resins are formed by reacting an organic polyepoxide with a tertiary amine salt. Such resins are described in U.S. Patent No. 3,962,165, column 2, lines 3 through 11, line 7; No. 3,975,346, column 1, lines 62 through 17, line 25; and No. 4,001,156, column 1, lines 37 through 16, line 7, parts of which are incorporated herein by reference. Other suitable cationic resins include ternary sulfonium salt group-containing resins, for example, those described in U.S. Patent No. 3,793,278, column 1, line 32 through column 5, line 20, parts of which are incorporated herein by reference. In addition, a cationic resin that is cured through an ester exchange mechanism, as described in European Patent Application No. 12463B1, page 2, line 1 to page 6, line 25, may also be used, and parts thereof are incorporated herein by reference.

[0044] Other suitable cationic base-containing film-forming polymers include those capable of forming a photodegradation-resistant electrodepositable coating composition. Such polymers include polymers comprising cationic amine salt groups derived from pendant and / or terminal amino groups disclosed in paragraphs

[0064] through

[0088] of U.S. Patent Application Publication No. 2003 / 0054193 A1, such portions thereof are incorporated herein by reference. Additionally, suitable disclosed in paragraphs

[0096] through

[0123] of U.S. Patent Application Publication No. 2003 / 0054193 A1 are active hydrogen-containing, cationic base-containing resins derived from polyglycidyl ethers of polyvalent phenols that are essentially devoid of aliphatic carbon atoms to which one or more aromatic groups are attached, such portions thereof are incorporated herein by reference.

[0045] Film-forming polymers containing active hydrogen-containing cationic bases are prepared as cationic and water-dispersible by at least partial neutralization using 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 a derivative thereof having the following chemical formula:

[0046]

[0047] Here, R is hydrogen or an alkyl group having 1 to 4 carbon atoms. Additionally, a mixture of the acids mentioned above may be used in the present disclosure.

[0048] The degree of neutralization of cationic base-containing film-forming polymers may vary depending on the specific polymer involved. However, sufficient acid must be used to adequately neutralize the cationic base-containing film-forming polymer 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 degree of neutralization. Additionally, an excess amount of acid may be used in excess of the amount required for 100% of the total theoretical degree of neutralization. For example, the amount of acid used to neutralize the cationic base-containing film-forming polymer is based on the total amines in the active hydrogen-containing cationic base-containing film-forming polymer. It may be. Alternatively, the amount of acid used to neutralize the active hydrogen-containing cationic base-containing film-forming polymer is based on the total amine in the active hydrogen-containing cationic base-containing film-forming polymer. The total amount of acid used to neutralize the cationic base-containing film-forming polymer may be in a range between any combination of the values ​​mentioned in the previous sentence, including the values ​​mentioned. For example, the total amount of acid used to neutralize the active hydrogen-containing cationic base-containing film-forming polymer may be 20%, 35%, 50%, 60%, or 80% based on the total amine in the cationic base-containing film-forming polymer.

[0049] The cationic base-containing film-forming polymer may be present in the cationic electrodepositable coating composition in an amount of at least 40% by weight, e.g., at least 50% by weight, e.g., at least 60% by weight, based on the total weight of the resin solid of the electrodepositable coating composition. The cationic base-containing film-forming polymer may be present in the cationic electrodepositable coating composition in an amount of 90% by weight or less, e.g., 80% by weight or less, e.g., 75% by weight or less, based on the total weight of the resin solid of the electrodepositable coating composition. The cationic base-containing film-forming polymer may be present in the cationic electrodepositable coating composition in an amount of 40% to 90% by weight, e.g., 40% to 80% by weight, e.g., 40% to 75% by weight, e.g., 50% to 90% by weight, e.g., 50% to 80% by weight, e.g., 50% to 75% by weight, e.g., 60% to 90% by weight, e.g., 60% to 80% by weight, e.g., 60% to 75% by weight, based on the total weight of the resin solid of the electrodepositable coating composition.

[0050] The "resin solid" as used herein comprises an ionic base-containing film-forming polymer, a curing agent, an addition polymer, and any additional water-dispersible non-coloring component(s) present in the electrodepositable coating composition.

[0051] Film-forming polymers containing ionic bases may include film-forming polymers containing anionic bases. As used herein, the term "film-forming polymer containing anionic bases" refers to an anionic polymer containing at least partially neutralized anionic functional groups that impart a negative charge, e.g., carboxylic acid groups and phosphate groups. As used herein, the term "polymer" includes, but is not limited to, both oligomers, homopolymers, and copolymers. Film-forming polymers containing anionic bases may include active hydrogen functional groups. As used herein, the term "active hydrogen functional group" refers to a group that is reactive with isocyanates as determined by the Zerewitinoff test as discussed above, and includes, e.g., hydroxyl groups, primary or secondary amine groups, and thiol groups. Film-forming polymers containing anionic bases that include active hydrogen functional groups may be referred to as film-forming polymers containing active hydrogen. Anionic base-containing film-forming polymers can be used in anionic electrodepositable coating compositions.

[0052] Anionic base-containing film-forming polymers may comprise base-solubilized carboxylic acid group-containing film-forming polymers, e.g., reaction products or adducts of a dry oil or semi-dry fatty acid ester with a dicarboxylic acid or anhydride; and reaction products of any additional unsaturated modified material that further reacts with the fatty acid ester, unsaturated acid or anhydride, and polyol. Also suitable are at least partially neutralized copolymers of unsaturated carboxylic acids, unsaturated carboxylic acids, and at least one other ethylene-based unsaturated monomer hydroxyalkyl ester. Another suitable anionic electrodepositing resin comprises an alkyd-aminoplast vehicle, i.e., a vehicle containing an alkyd resin and an amine-aldehyde resin. Another suitable anionic electrodepositing resin composition comprises a mixed ester of a resinous polyol. Other acid-functional polymers, e.g., phosphated polyepoxides or phosphated acrylic polymers, may be used. Exemplary phosphated polyepoxides are disclosed in paragraphs

[0004] through

[0015] of U.S. Patent Application Publication No. 2009-0045071 and paragraphs

[0014] through

[0040] of Application No. 13 / 232,093, the cited portions of which are incorporated herein by reference. Additionally, resins comprising one or more pendant carbamate functional groups, such as those described in U.S. Patent No. 6,165,338, are suitable.

[0053] The anionic base-containing film-forming polymer may be present in the anionic electrodepositable coating composition in an amount of at least 50% by weight, e.g., at least 55% by weight, e.g., at least 60% by weight, based on the total weight of the resin solid of the electrodepositable coating composition. The anionic base-containing film-forming polymer may be present in the anionic electrodepositable coating composition in an amount of 90% by weight or less, e.g., 80% by weight or less, e.g., 75% by weight or less, based on the total weight of the resin solid of the electrodepositable coating composition. The anionic base-containing film-forming polymer may be present in the anionic electrodepositable coating composition in an amount of 50% to 90% by weight, e.g., 50% to 80% by weight, e.g., 50% to 75% by weight, e.g., 55% to 90% by weight, e.g., 55% to 80% by weight, e.g., 55% to 75% by weight, e.g., 60% to 90% by weight, e.g., 60% to 80% by weight, e.g., 60% to 75% by weight, based on the total weight of the resin solid of the electrodepositable coating composition.

[0054] The ionic base-containing film-forming polymer may be present in the electrodeposited coating composition in an amount of at least 40% by weight, e.g., at least 50% by weight, e.g., at least 55% by weight, e.g., at least 60% by weight, based on the total weight of the resin solids of the electrodeposited coating composition. The ionic base-containing film-forming polymer may be present in the electrodeposited coating composition in an amount of 90% by weight or less, e.g., 80% by weight or less, e.g., 75% by weight or less, based on the total weight of the resin solids of the electrodeposited coating composition. The ionic base-containing film-forming polymer may be present in the electrodeposited coating composition in an amount of 40% to 90% by weight, e.g., 40% to 80% by weight, e.g., 40% to 75% by weight, e.g., 50% to 90% by weight, e.g., 50% to 80% by weight, e.g., 50% to 75% by weight, e.g., 55% to 90% by weight, e.g., 55% to 80% by weight, e.g., 55% to 75% by weight, e.g., 60% to 90% by weight, e.g., 60% to 80% by weight, e.g., 60% to 75% by weight, e.g., 60% to 75% by weight, based on the total weight of the resin solid of the electrodeposited coating composition.

[0055] Blocked polyisocyanate curing agent

[0056] The electrodepositable coating composition of the present disclosure further comprises a blocked polyisocyanate curing agent.

[0057] As used herein, “blocked polyisocyanate” means a polyisocyanate in which at least a portion of the isocyanate groups are blocked by a blocker introduced by the reaction of the free isocyanate groups of the polyisocyanate with a blocker. “Blocked” means that the isocyanate groups are reacted with the blocker such that the resulting blocked isocyanate groups are stable to active hydrogen at ambient temperatures, e.g., room temperature (about 23°C), but are reactive to active hydrogen of the film-forming polymer at elevated temperatures, such as 90°C to 200°C. Accordingly, a blocked polyisocyanate curing agent comprises a polyisocyanate that has reacted with one or more blockers. As used herein, “blocker” refers to a compound comprising a functional group reactive to the isocyanato group present on the polyisocyanate, which results in the binding of a residual moiety of the blocker to the isocyanato group so that the isocyanato group is stable to the active hydrogen functional group at room temperature (i.e., 23°C). The bound residual moiety of the blocker to the isocyanato group that provides stability of the isocyanato group to the active hydrogen functional group at room temperature is referred to herein as the “blocker.” The blocker can be identified by a reference to the blocker from which the blocker is derived by reaction with the isocyanato group. The blocker can be removed under suitable conditions, such as a rise in temperature, so that free isocyanato groups can be generated from the blocked isocyanato group. Thus, the reaction with the blocker can be reversed at a rise in temperature so that the previously blocked isocyanato group reacts freely with the active hydrogen functional group. As used herein, the term “derived from” in relation to a blocking polyisocyanate circuit breaker is intended to refer to the presence of a blocking agent residue within the circuit breaker, and is not intended to be limited to a circuit breaker produced by the reaction between the blocking agent and the isocyanate groups of the polyisocyanate.Accordingly, the blockers of the present disclosure produced from a synthetic route that does not involve a direct reaction between the isocyanato group and the blocker will still be considered to be "derived" from the blocker. Accordingly, the term "blocker" may also be used to refer to a blocked polyisocyanate moiety that generates free isocyanato groups by disengaging the blocker during curing. As used herein, the term “blocked” polyisocyanate curing agent collectively refers to a polyisocyanate curing agent that is completely blocked and a polyisocyanate curing agent that is at least partially blocked. As used herein, “completely blocked polyisocyanate curing agent” refers to a polyisocyanate in which each isocyanato group is blocked by a blocker. As used herein, “at least partially blocked polyisocyanate curing agent” refers to a polyisocyanate in which at least a portion of the isocyanato groups is blocked by a blocker, while the remaining isocyanato groups react with a portion of the polymer backbone.

[0058] A blocked polyisocyanate curing agent forms a coating by achieving curing of a coating composition containing reactive groups of an ionic base-containing film-forming polymer, such as active hydrogen groups and isocyanato groups reactive to them. The terms "cured," "cured," or similar terms used herein in relation to the electrodepositable coating compositions described herein mean that at least a portion of the components forming the electrodepositable coating composition are crosslinked to form a coating. Additionally, the curing of the electrodepositable coating composition refers to treating said composition under curing conditions (e.g., increased temperature) to cause the unblocking of the blocked isocyanato groups of the blocked polyisocyanate curing agent, thereby causing a reaction between the unblocked isocyanato groups of the polyisocyanate curing agent and the active hydrogen functional groups of the film-forming polymer, and consequently causing crosslinking of the components of the electrodepositable coating composition and the formation of at least a partially cured coating. The blocking agent removed during curing may be removed from the coating film by volatilization. Alternatively, some or all of the blocking agent may remain in the coating film after curing.

[0059] The polyisocyanates that can be used to manufacture curing agents for the blocked polyisocyanates of the present disclosure comprise any suitable polyisocyanates known in the art. The polyisocyanates are organic compounds comprising at least two, at least three, at least four, or more isocyanate functional groups, e.g., two, three, four or more isocyanate functional groups. For example, the polyisocyanates may comprise aliphatic and / or aromatic polyisocyanates. As can be understood, aromatic polyisocyanates will have a nitrogen atom of an isocyanate group covalently bonded to a carbon present in an aromatic group, and aliphatic polyisocyanates may contain an aromatic group indirectly bonded to an isocyanate group through a non-aromatic hydrocarbon group. Aliphatic polyisocyanates are, for example, (i) alkylene isocyanates, e.g., 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, e.g., 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,2-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexyl isocyanate) ("HMDI"), 1,6-hexamethylene It may include a cyclotrimer of diisocyanate (also known as the isocyanurate trimer of HDI, marketed as Desmodur N3300 by Convestro AG) and meta-tetramethylxylylene diisocyanate (marketed as TMXDI® by Allnex SA).Aromatic polyisocyanates may include, for example, (i) arylene isocyanates, e.g., m-phenylene diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate and 1,4-naphthalene diisocyanate, and (ii) alkalylene isocyanates, e.g., 4,4'-diphenylene methane diisocyanate ("MDI"), 2,4-tolylene or 2,6-tolylene diisocyanate ("TDI"), or a mixture thereof, 4,4-toluidine diisocyanate and xylylene diisocyanate. Triisocyanates, e.g., triphenylmethane-4,4',4"-triisocyanate, 1,3,5-triisocyanatobenzene and 2,4,6-triisocyanatotoluene, tetraisocyanates, e.g., 4,4'-diphenyldimethylmethane-2,2',5,5'-tetraisocyanate, may be included, and polymerized polyisocyanates, e.g., tolylene diisocyanate dimers and trimers, etc., may also be used. The blocked polyisocyanate curing agent may also include polymeric polyisocyanates, e.g., polymeric HDI, polymeric MDI, polymeric isophorone diisocyanate, etc. The curing agent may also include a blocked trimer of hexamethylene diisocyanate, which is available from Covestro AG as Desmodur N3300®. A mixture of polyisocyanate curing agents can also be used.

[0060] As discussed above, the isocyanato groups of the polyisocyanate are blocked by a blocking agent so that the blocked polyisocyanate curing agent contains the blocking agent. The blocking agent can be formed by reacting the isocyanato groups with a molar ratio of the blocking agent. For example, the isocyanato groups can be reacted at a 1:1 molar ratio of isocyanato groups to blocking agent so that the isocyanato groups are theoretically 100% blocked by the blocking agent. Alternatively, the molar ratio of isocyanato groups to blocking agent can be such that the isocyanato groups or the blocking agent are in excess. The blocking agent itself is a urethane group containing residues of the blocking agent and the isocyanato groups.

[0061] The blocker may include 1,2-polyol. The 1,2-polyol will react with the isocyanato groups of the polyisocyanate to form a blocker. The 1,2-polyol may be included in an amount of at least 30%, e.g., at least 35%, e.g., at least 40%, e.g., at least 45%, e.g., at least 50%, e.g., at least 55%, e.g., at least 60%, e.g., at least 65%, e.g., at least 70%, e.g., at least 75%, e.g., at least 80%, e.g., at least 85%, e.g., at least 90%, e.g., at least 95%, e.g., at least 99%, e.g., 100%, based on the total number of blockers. The 1,2-polyol may be included in an amount of 100% or less, e.g., 99% or less, e.g., 95% or less, e.g., 90% or less, e.g., 85% or less, e.g., 80% or less, e.g., 75% or less, e.g., 70% or less, e.g., 65% or less, e.g., 60% or less, e.g., 55% or less, e.g., 50% or less, e.g., 45% or less, e.g., 40% or less, e.g., 35% or less, e.g., 30% or less. Based on the total number of circuit breakers, the 1,2-polyol comprises 30% to 100% of the circuit breakers of the blocked polyisocyanate curing agent, e.g., 30% to 100%, e.g., 35% to 100%, e.g., 40% to 100%, e.g., 45% to 100%, e.g., 50% to 100%, e.g., 55% to 100%, e.g., 60% to 100%, 65% to 100%, e.g., 70% to 100%, e.g., 75% to 100%, e.g., 80% to 100%, e.g., 85% to 100%, e.g., 90% to 100%, e.g., 95% to 100%, e.g., 30% to 95%, e.g., 35% to 95%, e.g., 40% to 95%, e.g. 45% to 95%, for example 50% to 95%, for example 55% to 95%, for example 60% to 95%, 65% to 95%,For example, 70% to 95%, for example, 75% to 95%, for example, 80% to 95%, for example, 85% to 95%, for example, 90% to 95%, for example, 30% to 90%, for example, 35% to 90%, for example, 40% to 90%, for example, 45% to 90%, for example, 50% to 90%, for example, 55% to 90%, for example, 60% to 90%, 65% to 90%, for example, 70% to 90%, for example, 75% to 90%, for example, 80% to 90%, 85% to 90%, for example, 30% to 85%, for example, 35% to 85%, for example, 40% to 85%, for example, 45% to 85%, for example, 50% to 85%, for example, 55% to 85%, for example 60% to 85%, 65% to 85%, for example 70% to 85%, for example 75% to 85%, for example 80% to 85%, for example 30% to 80%, for example 35% to 80%, for example 40% to 80%, for example 45% to 80%, for example 50% to 80%, for example 55% to 80%, for example 60% to 80%, 65% to 80%, for example 70% to 80%, for example 75% to 80%, for example 30% to 75%, for example 35% to 75%, for example 40% to 75%, for example 45% to 75%, for example 50% to 75%, for example 55% to 75%, for example 60% to 75%, for example 65% to 75%, for example 70% to 75%, for example 30% to 70%, for example 35% to 70%, for example 40% to 70%, for example 45% to 70%, for example 50% to 70%, for example 55% to 70%, for example 60% to 70%, 65% to 70%, for example 30% to 65%, for example 35% to 65%, for example 40% to 65%, for example 45% to 65%, for example 50% to 65%, for example 55% to 65%, for example 60% to 65%, for example 30% to 60%,For example, it may be included in 35% to 60%, for example, 40% to 60%, for example, 45% to 60%, for example, 50% to 60%, for example, 55% to 60%, for example, 30% to 55%, for example, 35% to 55%, for example, 40% to 55%, for example, 45% to 55%, for example, 50% to 55%, for example, 30% to 50%, for example, 35% to 50%, for example, 40% to 50%, for example, 45% to 50%, for example, 30% to 45%, for example, 35% to 45%, for example, 40% to 45%, for example, 30% to 40%, for example, 35% to 40%, for example, 30% to 35%. As used herein, the percentage of blockers in a polyisocyanate curing agent blocked by a blocker refers to the molar percentage of isocyanato groups blocked by the blocker divided by the total number of isocyanato groups actually blocked, i.e., the total number of blockers. The percentage of blockers can be determined by dividing the total moles of blockers blocked by a specific blocker by the total moles of blockers in the polyisocyanate curing agent blocked and multiplying by 100. This may be expressed as the equivalent of the blocker relative to the total equivalent of isocyanato groups from the polyisocyanate, and the percentage and equivalent may be converted or used interchangeably (e.g., 40% of the total blockers is equivalent to 4 / 10 equivalent). For clarity, when there is a reference to blockers blocked by a blocker, the blockers do not strictly need to be derived from the reaction between the isocyanato groups and the blocker, but may be produced by any synthetic route as discussed below.

[0062] 1,2-polyols may include 1,2-alkanediols. Non-limiting examples of 1,2-alkanediols include ethylene glycol, propylene glycol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,2-heptanediol, 1,2-octanediol, glycerol esters or ethers having a 1,2-dihydroxyl functional group, and may include combinations thereof.

[0063] As discussed above, the isocyanato groups of the polyisocyanate are blocked by a blocking agent so that the blocked polyisocyanate curing agent includes the blocking agent to produce a urethane-containing compound. Accordingly, the blocked polyisocyanate curing agent may be referred to as the resulting structure that occurs after the reaction of the isocyanato group and the blocking agent, and the blocked polyisocyanate curing agent may include the following structure:

[0064]

[0065] Here, R is hydrogen or a substituted or unsubstituted alkyl group comprising 1 to 8 carbon atoms, e.g., 1 to 6 carbon atoms, wherein the substituted alkyl group optionally comprises an ether or ester functional group.

[0066] Although blocked polyisocyanate curing agents are generally disclosed as being produced by the reaction of an isocyanato group with a blocking agent, it should be understood that the blocked polyisocyanate curing agents of this disclosure can be produced using any synthetic route that produces a blocked polyisocyanate curing agent of the above structure. For example, as shown in the reaction scheme below, the isocyanato group of the polyisocyanate (the remainder of the polyisocyanate is referred to as "X") may react with the hydroxyl group of a hydroxyl-functional and epoxide-functional compound, and subsequently, the resulting epoxide group reacts with a hydroxyl-containing compound (where R is an alkyl group).

[0067]

[0068] In addition to the 1,2-polyol, the blocked polyisocyanate may optionally further comprise a co-blocker. The co-blocker may comprise any suitable blocker. The co-blocker may comprise aliphatic, alicyclic, or aromatic alkyl monoalcohols or phenolic compounds, for example, lower aliphatic alcohols, e.g., methanol, ethanol, and n-butanol; alicyclic alcohols including alicyclic monoalcohols such as cyclohexanol; hetero-alicyclic monoalcohols, e.g., solketal (DL-1,2-isopropylideneglycerol); aromatic-alkyl alcohols, e.g., phenylcarbinol and methylphenylcarbinol; and phenolic compounds, e.g., phenol itself and substituted phenols, e.g., cresol and nitrophenol, in which the substituents do not affect the coating operation. Additionally, glycol ethers and glycol amines may be used as blockers. Suitable glycol ethers include ethylene glycol butyl ether, diethylene glycol butyl ether, ethylene glycol methyl ether, and propylene glycol methyl ether. Other suitable blocking agents include oximes, e.g., methyl ethyl ketoxime, acetone oxime, and cyclohexanone oxime. Other co-blockers include 1,3-alkane diols, such as 1,3-butanediol; benzyl alcohols, e.g., benzyl alcohol; allyl alcohols, e.g., allyl alcohol; caprolactam; dialkylamines, e.g., dibutylamine; other diols, triols, or polyols; and mixtures thereof.

[0069] The co-blocker may comprise at least 1%, e.g., at least 5%, e.g., at least 10%, e.g., at least 15%, e.g., at least 20%, e.g., at least 25%, e.g., at least 30%, e.g., at least 45%, e.g., at least 50%, e.g., at least 55%, e.g., at least 60%, e.g., at least 65%, e.g., 70% of the blocked polyisocyanate curing agent based on the total number of circuit breakers. The co-blocker may comprise 70% or less, e.g., 65% or less, e.g., 60% or less, e.g., 55% or less, e.g., 50% or less, e.g., 45% or less, e.g., 40% or less, e.g., 35% or less, e.g., 30% or less, e.g., 25% or less, e.g., 20% or less, e.g., 15% or less, e.g., 10% or less, e.g., 5% or less, e.g., 1% or less, e.g., 1% or less, based on the total number of circuit breakers. The common circuit breaker is based on the total number of circuit breakers and is 1% to 70%, e.g., 5% to 70%, e.g., 10% to 70%, e.g., 15% to 70%, e.g., 20% to 70%, e.g., 25% to 70%, e.g., 30% to 70%, e.g., 35% to 70%, e.g., 40% to 70%, e.g., 45% to 70%, e.g., 50% to 70%, e.g., 55% to 70%, e.g., 60% to 70%, e.g., 65% to 70%, e.g., 1% to 65%, e.g., 5% to 65%, e.g., 10% to 65%, e.g., 15% to 65%, e.g., 20% to 65%, e.g., 25% to 65%, e.g., 30% to 65%, e.g., 35% to 65%, e.g., 40% to 65%, e.g., 45% to 65%, e.g., 50% to 65%, e.g., 55% to 65%, e.g., 60% to 65%, e.g., 1% to 60%, e.g., 5% to 60%, e.g., 10% to 60%, e.g., 15% to 60%, e.g., 20% to 60%, e.g.,25% to 60%, e.g., 30% to 60%, e.g., 35% to 60%, e.g., 40% to 60%, e.g., 45% to 60%, e.g., 50% to 60%, e.g., 55% to 60%, e.g., 1% to 55%, e.g., 5% to 55%, e.g., 10% to 55%, e.g., 15% to 55%, e.g., 20% to 55%, e.g., 25% to 55%, e.g., 30% to 55%, e.g., 35% to 55%, e.g., 40% to 55%, e.g., 45% to 55%, e.g., 50% to 55%, e.g., 1% to 50%, e.g., 5% to 50%, e.g., 10% to 50%, For example, 15% to 50%, for example, 20% to 50%, for example, 25% to 50%, for example, 30% to 50%, for example, 35% to 50%, for example, 40% to 50%, for example, 45% to 50%, for example, 1% to 45%, for example, 5% to 45%, for example, 10% to 45%, for example, 15% to 45%, for example, 20% to 45%, for example, 25% to 45%, for example, 30% to 45%, for example, 35% to 45%, for example, 40% to 45%, for example, 1% to 40%, for example, 5% to 40%, for example, 10% to 40%, for example, 15% to 40%, for example, 20% to 40%, for example, 25% to 40%, for example, 30% to 40%, for example, 35% to 40%, for example, 1% to 35%, for example, 5% to 35%, for example, 10% to 35%, for example, 15% to 35%, for example, 20% to 35%, for example, 25% to 35%, for example, 30% to 35%, for example, 1% to 30%, for example, 5% to 30%, for example, 10% to 30%, for example, 15% to 30%, for example, 20% to 30%, for example, 25% to 30%, for example, 1% to 25%, for example, 5% to 25%,For example, it includes 10% to 25%, for example, 15% to 25%, for example, 20% to 25%, for example, 1% to 20%, for example, 5% to 20%, for example, 10% to 20%, for example, 15% to 20%, for example, 1% to 15%, for example, 5% to 15%, for example, 10% to 15%, for example, 1% to 10%, for example, 5% to 10%, for example, 1% to 5%.

[0070] Blocked polyisocyanate curing agents may be substantially, essentially, or completely free of breaker units comprising polyester diol breaker units formed from the reaction of ethylene glycol, propylene glycol, or 1,4-butanediol with oxalic acid, succinic acid, adipic acid, suberic acid, or sebacic acid. A blocked polyisocyanate is substantially free of such breaker units if the breaker units comprising polyester diol units are present in an amount of 3% or less of the total number of breaker units. A blocked polyisocyanate is essentially free of such breaker units if the breaker units comprising polyester diol units are present in an amount of 1% or less of the total number of breaker units. A blocked polyisocyanate is completely free of such breaker units if the breaker units comprising polyester diol units are not present in the total number of breaker units, i.e., 0%.

[0071] Blocked polyisocyanate curing agents may include blockers derived from blockers comprising alpha-hydroxyamides, esters, or thioesters. As used herein, the term “alpha-hydroxyamide” refers to an organic compound having at least one alpha-hydroxyamide moiety comprising a hydroxyl functional group covalently bonded to the alpha-carbon of an amide group. As used herein, the term “alpha-hydroxy ester” refers to an organic compound having at least one alpha-hydroxy ester moiety comprising a hydroxyl functional group covalently bonded to the alpha-carbon of an ester group. As used herein, the term “alpha-hydroxythioester” refers to an organic compound having at least one alpha-hydroxythioester moiety comprising a hydroxyl functional group covalently bonded to the alpha-carbon of a thioester group. Blockers comprising alpha-hydroxyamides, esters, or thioesters may include compounds of Formula I:

[0072]

[0073] In the above equation, X is N(R2), O, S; n is 1 to 4; and when n = 1 and X = N(R2), R is hydrogen, C1 to C 10 It is an alkyl group, an aryl group, a polyether, a polyester, a polyurethane, a hydroxy-alkyl group, or a thio-alkyl group; and where n = 1 and X = O or S, R is C1 to C 10 It is an alkyl group, an aryl group, a polyether, a polyester, a polyurethane, a hydroxy-alkyl group, or a thio-alkyl group; and when n = 2 to 4, R is a polyvalent C1 to C 10 alkyl group, polyvalent aryl group, polyvalent polyether, polyvalent polyester, polyvalent polyurethane; each R1 is independently hydrogen, C1 to C 10 It is an alkyl group, an aryl group, or a cycloaliphatic group; each R2 is independently hydrogen, C1 to C10 It is an alkyl group, an aryl group, a cycloaliphatic group, a hydroxyalkyl group, or a thioalkyl group; R and R2 together can form a cycloaliphatic, heterocyclic structure. The cycloaliphatic, heterocyclic structure may include, for example, morpholine, piperidine, or pyrrolidine. It should be noted that R can be hydrogen only when X is N(R2).

[0074] As used herein, "alkyl" refers to a hydrocarbon chain that may be linear or branched and may include one or more non-aromatic hydrocarbon rings. As used herein, "aryl" refers to a hydrocarbon having a delocalized conjugated π-system having alternating double and single bonds between carbon atoms forming one or more coplanar hydrocarbon rings. As used herein, "alicyclonic" refers to a hydrocarbon containing one or more non-aromatic hydrocarbon rings. As used herein, the term "polyether" refers to a hydrocarbon having two or more ether groups and may optionally include other functional groups, e.g., hydroxyl groups or amino groups. As used herein, the term "polyester" refers to a hydrocarbon compound having two or more esters and may optionally include other functional groups, e.g., hydroxyl groups or amino groups. The term "polyurethane" as used herein refers to a hydrocarbon compound having two or more urethane groups and may optionally include other functional groups, such as hydroxyl groups or amino groups. The term "hydroxy-alkyl group" as used herein refers to an alkyl group having a hydroxyl functional group. The term "thio-alkyl group" as used herein refers to an alkyl group having a thio functional group.

[0075] Alpha-hydroxyamide blockers may comprise substituted glycolamides. As used herein, the term "substituted glycolamide" refers to a glycolamide compound having at least one hydrogen atom bonded to a nitrogen atom substituted with a substituent such as a monovalent organic group. In relation to structure (I), the substituted glycolamide is such that X is N (R2); R1 is hydrogen; and each R2 is independently hydrogen, C1 to C 10 It is an alkyl group, an aryl group, a cycloaliphatic group, a hydroxyalkyl group, or a thioalkyl group; R is C1 to C 10 Compounds comprising alkyl groups, aryl groups, alicyclic groups, polyethers, polyesters, polyurethanes, hydroxyalkyl groups, or thioalkyl groups. Accordingly, substituted glycolamides may include alkyl glycolamides, aryl glycolamides, polyether glycolamides, polyester glycolamides, polyurethane glycolamides, hydroxyalkyl glycolamides, or thioalkyl glycolamides. Each of these compounds may be monosubstituted or dissubstituted, for example, with respect to alkyl glycolamides, such as monoalkyl glycolamides or dialkyl glycolamides. Specific, non-limiting examples of mono-alkyl glycolamides include methyl glycolamide, ethyl glycolamide, propyl glycolamide, isopropyl glycolamide, butyl glycolamide, pentyl glycolamide, hexyl glycolamide, heptyl glycolamide, octyl glycolamide, ethyl-hexyl glycolamide, nonyl glycolamide, decyl glycolamide, etc., and specific examples of di-alkyl glycolamides include any one of monoalkyl glycolamides having an additional alkyl substituent, e.g., dimethyl glycolamide, di-ethyl glycolamide, dibutyl glycolamide, dipentyl glycolamide, etc.

[0076] Additionally, the substituted glycolamide blocker may include two or more glycolamide groups with respect to structure (I), such as when n is greater than 1. When n is 1, the R group is monovalent, and when n is greater than 1, the R group is polyvalent, for example, polyvalent C1 to C 10 It must be understood that it is an alkyl group, an aryl group, a cycloaliphatic group, a polyether, a polyester, or a polyurethane polymer.

[0077] Alpha-hydroxyamide blockers may comprise substituted lactoamides. As used herein, the term "substituted lactoamide" refers to a lactoamide compound having at least one hydrogen atom bonded to a nitrogen atom substituted with a substituent such as a monovalent organic group. With respect to structure (I), the substituted lactoamide is such that X is N(R2); R1 is methyl; and each R2 is independently hydrogen, C1 to C 10 It is an alkyl group, an aryl group, a cycloaliphatic group, a hydroxyalkyl group, or a thioalkyl group; R is C1 to C 10Compounds comprising alkyl groups, aryl groups, alicyclic groups, polyethers, polyesters, polyurethanes, hydroxyalkyl groups, or thioalkyl groups. Accordingly, substituted lactamides may include alkyl lactamides, aryl lactamides, polyether lactamides, polyester lactamides, polyurethane lactamides, hydroxyalkyl lactamides, or thioalkyl lactamides. Each of these compounds may be monosubstituted or dissubstituted, for example, with respect to alkyl lactamides, such as monoalkyl lactamides or dialkyl lactamides. Specific, non-limiting examples of mono-alkyl lactamides include methyl lactamide, ethyl lactamide, propyl lactamide, isopropyl lactamide, butyl lactamide, pentyl lactamide, hexyl lactamide, heptyl lactamide, octyl lactamide, ethyl-hexyl lactamide, nonyl lactamide, decyl lactamide, etc., and specific examples of di-alkyl lactamides include di-methyl lactamide, di-ethyl lactamide, di-propyl lactamide, di-butyl lactamide, di-pentyl lactamide, di-hexyl lactamide, etc.

[0078] Additionally, the substituted lactoamide blocker may include two or more lactoamide groups with respect to structure (I), such as when n is greater than 1. When n is 1, the R group is monovalent, and when n is greater than 1, the R group is polyvalent, for example, polyvalent C1 to C 10 It must be understood that it is an alkyl group, an aryl group, a cycloaliphatic group, a polyether, a polyester, or a polyurethane polymer.

[0079] The alkyl glycolamide or alkyl lactoamide circuit breaker of the present disclosure is, for example, structure:

[0080]

[0081] It may include a compound, where R1 is hydrogen or a methyl group; and R2 is C1 to C 10It is an alkyl group; R3 is hydrogen, and C1 to C 10 It is an alkyl group. R1 will be understood as the methyl group in alkyl lactoamide.

[0082] Non-limiting examples of blockers comprising alpha-hydroxyamides, esters or thioesters are described in paragraphs

[0012] through

[0026] of International Publication No. WO 2018 / 148306 A1, the cited portions of which are incorporated herein by reference.

[0083] As used herein, the term "multivalent" refers to an organic moiety having two or more bonding sites that covalently bond with other organic moietyes. For example, polyisocyanates are multivalent because they contain two or more isocyanato groups that covalently bond with other organic moietyes. Organic moietyes may be, for example, alkyl groups, alicyclic groups, aryl groups, polyethers, polyesters, polyurethanes, etc.

[0084] As used herein, the term "monovalent" refers to an organic moiety having one bonding site that covalently bonds with another organic moiety. Although it is used to refer to an organic moiety having only one bonding site, this does not exclude the presence of other functional groups that the organic moiety can bond to additional organic moietys, for example, during curing.

[0085] Blocked polyisocyanate curing agents may include tris(alkoxycarbonylamino)-1,3,5-triazine (TACT). Tris(alkoxycarbonylamino)-1,3,5-triazine has the structure:

[0086]

[0087] It may follow, wherein R1, R2, and R3 each independently comprise a C1-C8 alkyl group, e.g., a C1-C6 alkyl group, e.g., a C1-C4 alkyl group. In a non-limiting example, R1 and R2 are each methyl and R3 is n-butyl, or R 1 and R 2 are n-butyl and R 3 is methyl. In non-limiting examples, each radical R1, R2 and R3 is n-butyl. Suitable examples of tris(alkoxycarbonylamino)-1,3,5-triazine include tris(methoxycarbonylamino)-, tris(butoxycarbonylamino)-, and tris(2-ethylhexoxycarbonylamino)-1,3,5-triazine and any combination thereof.

[0088] The curing agent may be present in the electrodeposited coating composition in an amount of at least 10% by weight, e.g., at least 20% by weight, e.g., at least 25% by weight, based on the total weight of the resin solid of the electrodeposited coating composition. The curing agent may be present in the electrodeposited coating composition in an amount of 60% by weight or less, e.g., 50% by weight or less, e.g., 45% by weight or less, e.g., 40% by weight or less, based on the total weight of the resin solid of the electrodeposited coating composition. The curing agent may be present in the electrodepositable coating composition in an amount of 10% to 60% by weight, for example, 10% to 50% by weight, for example, 10% to 45% by weight, for example, 10% to 40% by weight, for example, 20% to 60% by weight, for example, 20% to 50% by weight, for example, 20% to 45% by weight, for example, 20% to 40% by weight, for example, 25% to 60% by weight, for example, 25% to 50% by weight, for example, 25% to 45% by weight, for example, 25% to 40% by weight, based on the total weight of the resin solid of the electrodepositable coating composition.

[0089] hardening catalyst

[0090] The electrodepositable coating composition further comprises a curing catalyst. As used herein, the term “curing catalyst” refers to a catalyst that promotes a transurethanation reaction and, in particular, promotes the unblocking of a blocked polyisocyanate blocker. The curing catalyst may optionally be a curing catalyst that does not contain tin, lead, iron, zinc, or manganese. Non-limiting examples of the curing catalyst include organic curing catalysts such as, but not limited to, amine-containing compounds; bismuth compounds or complexes; titanium compounds or complexes; zinc compounds or complexes; and combinations thereof.

[0091] The amine-containing curing catalyst may include any suitable amine-containing curing catalyst. For example, the amine-containing curing catalyst may include a guanidine curing catalyst, an imidazole curing catalyst, amidine, or any combination thereof.

[0092] It will be understood that "guanidine" as used herein refers to guanidine and derivatives thereof. For example, guanidine may include compounds, moiety and / or residues having the following general structure, and

[0093]

[0094] Herein, each R1, R2, R3, R4, and R5 (i.e., substituents of structural formula (III)) may comprise hydrogen, (cyclo)alkyl, aryl, aromatic, organometallic, or polymeric structures, or may together form cycloalkyl, aryl, or aromatic structures, wherein R1, R2, R3, R4, and R5 may be the same or different. As used herein, “(cyclo)alkyl” refers to both alkyl and cycloalkyl. Where any of the R groups “can together form (cyclo)alkyl, aryl, and / or aromatic groups,” this means that any two adjacent R groups are connected to form a cyclic moiety such as the ring of structural formulas (IV)–(VII) below.

[0095] It will be understood that the double bond between the carbon atom and the nitrogen atom shown in structural formula (III) can be located between the carbon atom and other nitrogen atoms of structural formula (III). Therefore, various substituents of structural formula (III) can be attached to different nitrogen atoms depending on where the double bond is located within the structural formula.

[0096] Guanidine may include cyclic guanidine such as guanidine of structural formula (III), wherein two or more R groups of structural formula (III) together form one or more rings. That is, cyclic guanidine > It may include 1 ring(s).

[0097] Cyclic guanidine may include bicyclic guanidine, and bicyclic guanidine may include 1,5,7-triazabicyclo[4.4.0]dek-5-en ("TBD" or "BCG").

[0098] Guanidine is present in the electrodepositable coating composition such that the weight ratio of bismuth metal to guanidine derived from the solubilized bismuth catalyst is 1.00:0.071 to 1.0:2.1, e.g. 1.0:0.17 to 1.0:2.0, e.g. 1.0:0.33 to 1.0:1.33, e.g. 1.0:0.47 to 1.0:1.0.

[0099] Guanidine is present in the electrodepositable coating composition such that the molar ratio of bismuth metal to guanidine is 1.0:0.25 to 1.0:3.0, e.g. 1:0.5 to 1.0:2.0, e.g. 1:0.7 to 1:1.5.

[0100] Surprisingly, it was found that the addition of guanidine to a bismuth-catalyzed electrodepositable coating composition produces an electrodepositable coating composition that maintains curing even when the concentration of phosphate ions increases. Sufficient curing performance can be maintained despite the presence of phosphate ions in the electrodepositable coating composition. For example, the electrodepositable coating composition can achieve curing together with phosphate ions present in the electrodepositable coating composition in an amount of 1 to 1,000 ppm, e.g., 1 to 800 ppm, e.g., 1 to 500 ppm, e.g., 1 to 300 ppm, e.g., 1 to 200 ppm, e.g., 100 to 1,000 ppm, e.g., 100 to 800 ppm, e.g., 100 to 500 ppm, e.g., 100 to 300 ppm, e.g., 100 to 200 ppm, e.g., 200 to 1,000 ppm, e.g., 200 to 800 ppm, e.g., 200 to 500 ppm, e.g., 200 to 300 ppm, e.g., 300 to 1,000 ppm, e.g., 300 to 800 ppm, e.g., 300 to 500 ppm. there is.

[0101] The imidazole curing catalyst may include an imidazole modified product as described in International Publication No. WO 2020 / 203311 A1.

[0102] The amidine curing catalyst may include 1,8-diazabicyclo[5.4.0]undec-7-en (DBU).

[0103] The amine-containing curing catalyst may be present in the coating composition in an amount of at least 0.1 wt%, e.g., at least 0.2 wt%, e.g., at least 0.5 wt%, e.g., at least 0.8 wt%, e.g., at least 1 wt%, e.g., at least 1.5 wt% based on the total weight of the resin solid of the coating composition. The amine-containing curing catalyst may be present in the coating composition in an amount of 7 wt% or less, e.g., 4 wt% or less, e.g., 2 wt% or less, e.g., 1.5 wt% or less, e.g., 1 wt% or less based on the total weight of the resin solid of the coating composition. The amine-containing curing catalyst is present in an amount of 0.1 wt% to 7 wt%, e.g., 0.1 wt% to 4 wt%, e.g., 0.1 wt% to 2 wt%, e.g., 0.1 wt% to 1.5 wt%, e.g., 0.1 wt% to 1 wt%, e.g., 0.2 wt% to 7 wt%, e.g., 0.2 wt% to 4 wt%, e.g., 0.2 wt% to 2 wt%, e.g., 0.2 wt% to 1.5 wt%, e.g., 0.2 wt% to 1 wt%, e.g., 0.5 wt% to 7 wt%, e.g., 0.5 wt% to 4 wt%, e.g., 0.5 wt% to 2 wt%, e.g., 0.5 wt% to 1.5 wt%, e.g., 0.5 wt% to 1 wt%, e.g., 0.8 wt% to 7 wt%, e.g., based on the total weight of the resin solid of the coating composition. It may be present in the coating composition in an amount of 0.8 wt% to 4 wt%, e.g., 0.8 wt% to 2 wt%, e.g., 0.8 wt% to 1.5 wt%, e.g., 0.8 wt% to 1 wt%, e.g., 1 wt% to 7 wt%, e.g., 1 wt% to 4 wt%, e.g., 1 wt% to 2 wt%, e.g., 1 wt% to 1.5 wt%, e.g., 1.5 wt% to 7 wt%, e.g., 1.5 wt% to 4 wt%, e.g., 1.5 wt% to 2 wt%.

[0104] Zinc-containing catalysts may include metal salts and / or zinc complexes. For example, zinc-containing hardening catalysts may include zinc (II) amidine complexes, zinc octoate, zinc naphthenate, zinc thalate, zinc carboxylate having about 8 to 14 carbons in a carboxylate group, zinc acetate, zinc sulfonate, zinc methanesulfonate, or any combination thereof.

[0105] The zinc(II) amidine complex contains amidine and a carboxylate ligand. More specifically, the zinc(II) amidine complex comprises a compound of the formula Zn(A)2(C)2, where A represents amidine and C represents a carboxylate. More specifically, A can be represented by formula (1) or formula (2), and

[0106]

[0107] Here, R 1 and R 3 Each is an organic group attached independently via hydrogen or carbon atoms, or mutually Connected by links to form a complex ring having one or more heteroatoms or a fused bicyclic ring having one or more heteroatoms; R 2 is a hydrogen, an organic group attached via a carbon atom, an optionally substituted amine group, or a hydroxyl group optionally etherified to a hydrocarbyl group having up to 8 carbon atoms; R 4 is a hydroxyl group that can be optionally etherified to an organic group attached via hydrogen or carbon atoms or a hydrocarbyl group having up to 8 carbon atoms; R 5 , R 6 , R 7 and R 8is a carbonamide group that is independently alkyl-substituted with hydrogen, alkyl-substituted alkyl hydroxyalkyl, aryl, aralkyl, cycloalkyl, heterocyclic, ether, thioether, halogen, ―N(R)2, polyethylene polyamine, nitro group, keto group, ester group, or alkyl-substituted alkyl hydroxyalkyl, aryl, aralkyl, cycloalkyl, heterocyclic, ether, thioether, halogen, ―N(R)2, polyethylene polyamine, nitro group, keto group, or ester group; C is an aliphatic, aromatic, or polymeric carboxylate having 45 to 465 equivalents.

[0108] The zinc-containing curing catalyst may be present in the coating composition in an amount of at least 0.1 wt%, e.g., at least 0.2 wt%, e.g., at least 0.5 wt%, e.g., at least 0.8 wt%, e.g., at least 1 wt%, e.g., at least 1.5 wt% based on the total weight of the resin solid of the coating composition. The zinc-containing curing catalyst may be present in the coating composition in an amount of 7 wt% or less, e.g., 4 wt% or less, e.g., 2 wt% or less, e.g., 1.5 wt% or less, e.g., 1 wt% or less based on the total weight of the resin solid of the coating composition. The zinc-containing curing catalyst is present in an amount of 0.1 wt% to 7 wt%, e.g., 0.1 wt% to 4 wt%, e.g., 0.1 wt% to 2 wt%, e.g., 0.1 wt% to 1.5 wt%, e.g., 0.1 wt% to 1 wt%, e.g., 0.2 wt% to 7 wt%, e.g., 0.2 wt% to 4 wt%, e.g., 0.2 wt% to 2 wt%, e.g., 0.2 wt% to 1.5 wt%, e.g., 0.2 wt% to 1 wt%, e.g., 0.5 wt% to 7 wt%, e.g., 0.5 wt% to 4 wt%, e.g., 0.5 wt% to 2 wt%, e.g., 0.5 wt% to 1.5 wt%, e.g., 0.5 wt% to 1 wt%, e.g., 0.8 wt% to 7 wt%, e.g., based on the total weight of the resin solid of the coating composition. It may be present in the coating composition in an amount of 0.8 wt% to 4 wt%, e.g., 0.8 wt% to 2 wt%, e.g., 0.8 wt% to 1.5 wt%, e.g., 0.8 wt% to 1 wt%, e.g., 1 wt% to 7 wt%, e.g., 1 wt% to 4 wt%, e.g., 1 wt% to 2 wt%, e.g., 1 wt% to 1.5 wt%, e.g., 1.5 wt% to 7 wt%, e.g., 1.5 wt% to 4 wt%, e.g., 1.5 wt% to 2 wt%.

[0109] According to the present disclosure, the curing catalyst may include a bismuth catalyst. As used herein, the term “bismuth catalyst” refers to a catalyst containing bismuth that promotes a transurethanation reaction and, in particular, promotes the unblocking of a blocked polyisocyanate curing agent blocker.

[0110] The bismuth catalyst may include a soluble bismuth catalyst. The "soluble" or "solubilized" bismuth catalyst used herein is a catalyst in which at least 35% of the bismuth catalyst dissolves in an aqueous medium having a pH in the range of 4 to 7 at room temperature (e.g., 23°C). The soluble bismuth catalyst may provide soluble bismuth metal in an amount of at least 0.04 weight% based on the total weight of the electrodeposited coating composition.

[0111] Alternatively, the bismuth catalyst may comprise an insoluble bismuth catalyst. The "insoluble" bismuth catalyst used herein is a catalyst in which less than 35% of the catalyst is soluble in an aqueous medium having a pH in the range of 4 to 7 at room temperature (e.g., 23°C). The insoluble bismuth catalyst may provide solubilized bismuth metal in an amount of less than 0.04 weight% based on the total weight of the electrodeposited coating composition.

[0112] The percentage of solubilized bismuth catalyst present in the composition can be determined by using ICP-MS to calculate the total amount of bismuth metal (i.e., soluble and insoluble) and the total amount of solubilized bismuth metal, and by calculating the percentage using these measurements.

[0113] Bismuth catalysts may include bismuth compounds and / or complexes.

[0114] Bismuth catalysts may include, for example, colloidal bismuth oxide or bismuth hydroxide, bismuth compound complexes, for example, bismuth chelate complexes, or bismuth salts of inorganic or organic acids, wherein the term “bismuth salt” includes salts containing bismuth cations and acid anions as well as bismuthoxy salts.

[0115] Examples of inorganic or organic acids from which bismuth salts can be derived are hydrochloric acid, sulfuric acid, nitric acid, inorganic or organic sulfonic acids, carboxylic acids, e.g. formic acid or acetic acid, aminocarboxylic acids and hydroxycarboxylic acids, e.g. lactic acid or dimethylolpropionic acid.

[0116] Non-limiting examples of bismuth salts include aliphatic hydroxycarboxylic acid salts of bismuth, e.g., bismuth lactate or dimethylolpropionate salts, e.g., bismuth lactate or bismuth dimethylolpropionate; bismuth subnitrate; bismuth amidosulfonic acid salts; bismuth hydroxysulfonic acid salts such as alkyl sulfonic acid salts including bismuth methanesulfonate. Further non-limiting examples of bismuth compounds or complex catalysts include bismuth oxide, bismuth carboxylate, bismuth sulfamate, bismuth sulfonate, and combinations thereof.

[0117] The bismuth catalyst may be present in an amount of 0.01 wt%, e.g., at least 0.1 wt%, e.g., at least 0.2 wt%, e.g., at least 0.5 wt%, e.g., at least 1 wt%, e.g., 1 wt%, based on the total resin solid weight of the composition. The bismuth catalyst may be present in an amount of 3 wt% or less of bismuth metal, e.g., 1.5 wt% or less, e.g., 1 wt% or less, based on the total resin solid weight of the composition. The bismuth catalyst may be present in an amount of 0.01 wt% to 3 wt% of bismuth metal, for example 0.1 wt% to 1.5 wt%, for example 0.2 wt% to 1 wt%, for example 0.5 wt% to 3 wt%, for example 0.5 wt% to 1.5 wt%, for example 0.5 wt% to 1 wt%, for example 1 wt% to 3 wt%, for example 1 wt% to 1.5 wt%, based on the total weight of the resin solids of the composition.

[0118] The bismuth catalyst may be present in an amount such that the amount of solubilized bismuth metal is at least 0.04 wt%, e.g., at least 0.06 wt%, e.g., at least 0.07 wt%, e.g., at least 0.08 wt%, e.g., at least 0.09 wt%, e.g., at least 0.10 wt%, e.g., at least 0.11 wt%, e.g., at least 0.12 wt%, e.g., at least 0.13 wt%, e.g., at least 0.14 wt% or more, based on the total weight of the electrodeposited coating composition. The bismuth catalyst may be present in an amount such that the amount of solubilized bismuth metal is 0.30 wt% or less, based on the total weight of the electrodeposited coating composition.

[0119] The bismuth catalyst may be present in an amount such that the amount of solubilized bismuth metal is at least 0.22 wt%, e.g., at least 0.30 wt%, e.g., at least 0.34 wt%, e.g., at least 0.40 wt%, e.g., at least 0.45 wt%, e.g., at least 0.51 wt%, e.g., at least 0.56 wt%, e.g., at least 0.62 wt%, e.g., at least 0.68 wt%, e.g., at least 0.73 wt%, e.g., at least 0.80 wt% or more, based on the total weight of the resin solid.

[0120] An electrodepositable coating composition may be substantially, essentially, or completely free of bismuth nitrite. As used herein, an electrodepositable coating composition is "substantially free" of bismuth nitrite if bismuth nitrite is present in an amount of at most less than 0.01 weight percent based on the total resin solid weight of the composition. As used herein, an electrodepositable coating composition is "essentially free" of bismuth nitrite if bismuth nitrite is present in a trace or incidental amount that is at most insufficient to affect any property of the composition, for example, less than 0.001 weight percent based on the total resin solid weight of the composition. As used herein, an electrodepositable coating composition is "completely free" of bismuth nitrite if bismuth nitrite is not present in the composition, i.e., 0.000 weight percent based on the total resin solid weight of the composition.

[0121] The electrodeposited coating composition may be substantially, essentially, or completely free of bismuth oxide. As used herein, the electrodeposited coating composition is "substantially free" of bismuth oxide if bismuth oxide is present in an amount of at most less than 0.01 weight percent based on the total weight of the resin solids of the composition. The electrodeposited coating composition used herein is "essentially free" of bismuth oxide if bismuth oxide is present in a trace or incidental amount that is insufficient to affect any property of the composition, for example, less than 0.001 weight percent based on the total weight of the resin solids of the composition. The electrodeposited coating composition used herein is "completely free" of bismuth oxide if bismuth oxide is not present in the composition, i.e., 0.000 weight percent based on the total weight of the resin solids of the composition.

[0122] The electrodeposited coating composition may be substantially, essentially, or completely free of bismuth silicate, bismuth titanate, bismuth sulfamate, and / or bismuth lactate. The electrodeposited coating composition used herein is "substantially free" of any of these substances if, where a substance is present, it is present in an amount of less than 0.01 weight percent based on the total resin solid weight of the composition (each individually). The electrodeposited coating composition used herein is "essentially free" of any of these substances if, where a substance is present, it is present in a trace or incidental amount insufficient to affect any property of the composition, for example, less than 0.001 weight percent based on the total resin solid weight of the composition (each individually). The electrodeposited coating composition used herein is "completely free" of any of these substances if a substance is not present in the composition, i.e., 0.000 weight percent based on the total resin solid weight of the composition (each individually).

[0123] Edge control add-on

[0124] The electrodepositable coating composition of the present disclosure further comprises an edge control adduct.

[0125] The term "edge control adjuvant" as used herein refers to a substance added in an additional amount (i.e., generally less than 15 weight percent based on the total weight of the resin solid) to improve the coverage of the coating on the edge of the substrate to which the coating is applied after the coating has cured. The edge control adjuvant can act by manipulating the flow of the binder component during curing.

[0126] The edge control adduct comprises (1) an addition polymer comprising a polymerization product of a polymeric dispersant and a second-stage ethylene-based unsaturated monomer composition comprising a second-stage hydroxyl-functional (meth)acrylamide monomer and / or a second-stage hydroxyl-functional (meth)acrylate monomer; (2) a hydroxyl-functional addition polymer comprising a constituent unit, wherein at least 70% is of Formula VIII:

[0127] ―[―C(R 1 )2―C(R 1 )(OH)―]― (VIII),

[0128] Includes and each R 1The hydroxyl functional addition polymer may independently comprise hydrogen, an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an alkylcycloalkyl group, a substituted alkylcycloalkyl group, a cycloalkylalkyl group, a substituted cycloalkylalkyl group, an aryl group, a substituted aryl group, an alkylaryl group, a substituted alkylaryl group, a cycloalkylaryl group, a substituted cycloalkylaryl group, an arylalkyl group, a substituted arylalkyl group, an arylcycloalkyl group, or a substituted arylcycloalkyl group, wherein the % is a hydroxyl functional addition polymer based on the total constituent unit of the hydroxyl functional addition polymer; (3) a cellulose derivative; (4) a polyvinyl formamide; (5) a cationic epoxy microgel; (6) a polyamine-dialdehyde adduct or any combination thereof.

[0129] As used herein, the term "addition polymer" refers to a polymerization product containing at least partially residues of an unsaturated monomer.

[0130] An addition polymer comprising a polymerization product of a polymeric dispersant and a second-stage ethylene-based unsaturated monomer composition comprising a second-stage hydroxyl-functional (meth)acrylamide monomer and / or a second-stage hydroxyl-functional (meth)acrylate monomer. : The edge control adduct may include an addition polymer comprising a polymerization product of a polymeric dispersant and a second-stage ethylene-based unsaturated monomer composition comprising a second-stage hydroxyl-functional (meth)acrylamide monomer and / or a second-stage hydroxyl-functional (meth)acrylate monomer.

[0131] The addition polymer may comprise an acrylic polymer comprising a polymerization product of a polymeric dispersant and an aqueous dispersion of a second-stage ethylene-based unsaturated monomer composition. As used herein, the term “acrylic polymer” refers to a polymerization product comprising at least partially residues of (meth)acrylic monomers. The polymerization product may be formed by a two-stage polymerization process, wherein the polymeric dispersant is polymerized during the first stage and the second-stage ethylene-based unsaturated monomer composition is added to the aqueous dispersion of the polymeric dispersant and polymerized in the presence of the polymeric dispersant participating in the polymerization to form an acrylic polymer during the second stage. Non-limiting examples of an acrylic polymer comprising a polymerization product of a polymeric dispersant and an aqueous dispersion of a second-stage ethylene-based unsaturated monomer composition are described in paragraphs

[0013] through

[0055] of International Publication No. WO 2018 / 160799 A1, the referenced portions of which are incorporated herein by reference.

[0132] The addition polymer may alternatively comprise a second-stage ethylene-based unsaturated monomer composition comprising a polymerization product of a polymeric dispersant and a second-stage (meth)acrylamide monomer.

[0133] The polymerization product can be formed by a two-step polymerization process, wherein a polymeric dispersant is polymerized during the first step, and in the second step, an ethylene-based unsaturated monomer composition is added to an aqueous dispersion of the polymeric dispersant and polymerized in the presence of a polymeric dispersant participating in polymerization to form an addition polymer during the second step.

[0134] The polymeric dispersant may include any polymeric dispersant having a sufficient base content to stably disperse and participate in the subsequent polymerization of the second-stage ethylene-based unsaturated monomer composition and to provide a stable resulting addition polymer in the electrodeposited coating composition. Although the polymeric dispersant polymerized during the first stage has been mentioned, a pre-formed or commercially available dispersant may be used, and it will be understood that the pre-formation of the polymeric dispersant is considered as the first-stage polymerization.

[0135] The polymeric dispersant polymerized during the first step may include the polymerization product of the first step ethylene-based unsaturated monomer composition.

[0136] The first-stage ethylene-based unsaturated monomer composition comprises one or more monomers that incorporate an ionic base into a polymeric dispersant such that the polymeric dispersant comprises an ionic base-containing polymeric dispersant. For example, the polymeric dispersant may include a cationic base such that the polymeric dispersant comprises a cationic base-containing polymeric dispersant, or may include an anionic base such that the polymeric dispersant comprises an anionic base-containing polymeric dispersant. The cationic base may be formed by the incorporation and subsequent neutralization of an epoxide-functional unsaturated monomer, an amino-functional unsaturated monomer, or a combination thereof. For example, the polymeric dispersant may comprise a cationic base-containing polymeric dispersant comprising a polymerization product of the first-stage ethylene-based unsaturated monomer composition comprising an epoxide-functional ethylene-based unsaturated monomer and / or an amino-functional ethylene-based unsaturated monomer. Anionic bases can be formed by the incorporation of acid-functional unsaturated monomers and subsequent neutralization. For example, a polymeric dispersant may include an anionic base-containing polymeric dispersant comprising a polymerization product of a first-stage ethylene-based unsaturated monomer composition comprising an acid-functional ethylene-based unsaturated monomer.

[0137] The first-stage ethylene-based unsaturated monomer composition may optionally include an epoxide-functional monomer. The epoxide-functional monomer allows the incorporation of epoxide functional groups into the polymeric dispersant. The epoxide functional groups can be converted into cationic bases through the reaction of the epoxide functional groups with amines and neutralization with acids. Examples of suitable 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 epoxide functional monomer may be present in an amount of 5% to 50% by weight, e.g., 5% to 40% by weight, e.g., 5% to 30% by weight, e.g., 5% to 25% by weight, e.g., 5% to 20% by weight, e.g., 10% to 50% by weight, e.g., 10% to 40% by weight, e.g., 10% to 30% by weight, e.g., 10% to 25% by weight, e.g., 10% to 20% by weight, e.g., 20% to 50% by weight, e.g., 20% to 40% by weight, e.g., 20% to 30% by weight, e.g., 20% to 25% by weight, based on the total weight of the first-stage ethylene-based unsaturated monomer composition.

[0138] The first-stage ethylene-based unsaturated monomer composition may optionally include an amino functional monomer. The amino functional monomer allows the incorporation of amino functional groups into the polymeric dispersant. The amino functional groups can be neutralized with an acid to be converted into cationic base groups. The amino functional monomer may include any suitable amino functional unsaturated monomer, such as, for example, N-alkylaminoalkyl (meth)acrylate, N,N-(dialkyl)aminoalkyl (meth)acrylate, aminoalkyl (meth)acrylate, etc. Specific, non-limiting examples of suitable amino-functional monomers include 2-aminoethyl (meth)acrylate, 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 amino functional monomer may be present in an amount of 5% to 50% by weight, e.g., 5% to 40% by weight, e.g., 5% to 30% by weight, e.g., 5% to 25% by weight, e.g., 5% to 20% by weight, e.g., 10% to 50% by weight, e.g., 10% to 40% by weight, e.g., 10% to 30% by weight, e.g., 10% to 25% by weight, e.g., 10% to 20% by weight, e.g., 20% to 50% by weight, e.g., 20% to 40% by weight, e.g., 20% to 30% by weight, e.g., 20% to 25% by weight, based on the total weight of the first-stage ethylene-based unsaturated monomer composition.

[0139] The first-stage ethylene-based unsaturated monomer composition may optionally include an acid-functional ethylene-based unsaturated monomer. The acid-functional monomer allows for neutralization with a base to incorporate anionic base groups into the polymeric dispersant. The acid-functional ethylene-based unsaturated monomer may include phosphoric acid or a carboxylic acid-functional ethylene-based unsaturated monomer, for example, (meth)acrylic acid. The acid-functional monomer may be present in the first-stage ethylene-based unsaturated monomer composition in an amount of at least 5% by weight, e.g., at least 10% by weight, e.g., at least 20% by weight, based on the total weight of the first-stage ethylene-based unsaturated monomer composition. The acid-functional monomer may be present in the first-stage ethylene-based unsaturated monomer composition in an amount of 50% by weight or less, e.g., 40% by weight or less, e.g., 30% by weight or less, e.g., 25% by weight or less, e.g., 20% by weight or less, based on the total weight of the first-stage ethylene-based unsaturated monomer composition. The acid functional monomer may be present in the first-stage ethylene-based unsaturated monomer composition in an amount of 5% to 50% by weight, e.g., 5% to 40% by weight, e.g., 5% to 30% by weight, e.g., 5% to 25% by weight, e.g., 5% to 20% by weight, e.g., 10% to 50% by weight, e.g., 10% to 40% by weight, e.g., 10% to 30% by weight, e.g., 10% to 25% by weight, e.g., 10% to 20% by weight, e.g., 20% to 50% by weight, e.g., 20% to 40% by weight, e.g., 20% to 30% by weight, e.g., 20% to 25% by weight, based on the total weight of the first-stage ethylene-based unsaturated monomer composition.

[0140] The first-stage ethylene-based unsaturated monomer composition is optionally C1-C 18It may further include at least one of an alkyl (meth)acrylate; a first-stage hydroxyl functional (meth)acrylate; a vinyl aromatic compound; and / or a monomer comprising two or more ethylene-based unsaturated groups per molecule.

[0141] The first-stage ethylene-based unsaturated monomer composition is optionally C1-C 18 It may further include monoolefinic aliphatic compounds such as alkyl (meth)acrylates. Suitable C1-C 18 Examples of alkyl (meth)acrylates include, but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, isodecyl (meth)acrylate, stearyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobornyl (meth)acrylate, t-butyl (meth)acrylate, etc. C1-C 18 The alkyl (meth)acrylate may be present in the first-stage ethylene-based unsaturated monomer composition in an amount of at least 30 wt%, e.g., at least 40 wt%, e.g., at least 50 wt%, e.g., at least 60 wt%, e.g., at least 70 wt% based on the total weight of the first-stage ethylene-based unsaturated monomer composition. C1-C 18 The alkyl (meth)acrylate may be present in the first-stage ethylene-based unsaturated monomer composition in an amount of 90 wt% or less, e.g., 80 wt% or less, e.g., 70 wt% or less, e.g., 60 wt% or less, based on the total weight of the first-stage ethylene-based unsaturated monomer composition. C1-C 18The alkyl (meth)acrylate is 30 wt% to 90 wt%, e.g., 30 wt% to 80 wt%, e.g., 30 wt% to 70 wt%, e.g., 30 wt% to 60 wt%, e.g., 40 wt% to 90 wt%, e.g., 40 wt% to 80 wt%, e.g., 40 wt% to 70 wt%, e.g., 40 wt% to 60 wt%, e.g., 50 wt% to 90 wt%, e.g., 50 wt% to 80 wt%, e.g., 50 wt% to 70 wt%, e.g., 50 wt% to 60 wt%, e.g., 50 wt% to 60 wt%, e.g., 60 wt% to 90 wt%, e.g., 60 wt% to 80 wt%, e.g., 60 wt% to 70 wt%, e.g., 70 wt% to It may be present in the first-stage ethylene-based unsaturated monomer composition in an amount of 90 weight%, for example, 70 weight% to 80 weight%. The term "(meth)acrylate" and similar terms as used herein include both acrylate and methacrylate.

[0142] The ethylene-based unsaturated monomer composition may optionally include hydroxyl-functional (meth)acrylates. As used herein, the term "hydroxyl-functional (meth)acrylate" collectively refers to both acrylates and methacrylates having a hydroxyl functional group, i.e., having at least one hydroxyl functional group in the molecule. Hydroxyl-functional (meth)acrylates include hydroxyalkyl (meth)acrylates, such as, for example, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, etc., as well as combinations thereof. The hydroxyl-functional (meth)acrylate may be present in the first-stage ethylene-based unsaturated monomer composition in an amount of at least 1% by weight, e.g., at least 5% by weight, e.g., at least 10% by weight, based on the total weight of the first-stage ethylene-based unsaturated monomer composition. The hydroxyl-functional (meth)acrylate may be present in the first-stage ethylene-based unsaturated monomer composition in an amount of 40% by weight or less, e.g., 30% by weight or less, e.g., 25% by weight or less, e.g., 15% by weight or less, based on the total weight of the first-stage ethylene-based unsaturated monomer composition.The hydroxyl functional (meth)acrylate may be present in the first-stage ethylene-based unsaturated monomer composition in an amount of 1% to 40% by weight, e.g., 1% to 30% by weight, e.g., 1% to 25% by weight, e.g., 1% to 15% by weight, e.g., 5% to 40% by weight, e.g., 5% to 30% by weight, e.g., 5% to 25% by weight, e.g., 5% to 15% by weight, e.g., 10% to 40% by weight, e.g., 10% to 30% by weight, e.g., 10% to 25% by weight, e.g., 10% to 15% by weight, based on the total weight of the first-stage ethylene-based unsaturated monomer composition.

[0143] The first stage ethylene-based unsaturated monomer composition may include a vinyl aromatic compound. Non-limiting examples of suitable vinyl aromatic compounds include styrene, alpha-methyl styrene, alpha-chloromethyl styrene, and / or vinyl toluene. The vinyl aromatic compound may be present in the first stage ethylene-based unsaturated monomer composition in an amount of at least 0.5 wt%, e.g., at least 1 wt%, e.g., at least 5 wt%, e.g., at least 10 wt% based on the total weight of the first stage ethylene-based unsaturated monomer composition. The vinyl aromatic compound may be present in the first stage ethylene-based unsaturated monomer composition in an amount of 40 wt% or less, e.g., 30 wt% or less, e.g., 20 wt% or less, e.g., 15 wt% or less, e.g., 10 wt% or less based on the total weight of the first stage ethylene-based unsaturated monomer composition. The vinyl aromatic compound is present in an amount of 0.5 wt% to 40 wt%, e.g., 0.5 wt% to 30 wt%, e.g., 0.5 wt% to 20 wt%, e.g., 0.5 wt% to 15 wt%, e.g., 0.5 wt% to 10 wt%, e.g., 1 wt% to 40 wt%, e.g., 1 wt% to 30 wt%, e.g., 1 wt% to 20 wt%, e.g., 1 wt% to 15 wt%, e.g., 1 wt% to 10 wt%, e.g., 5 wt% to 40 wt%, e.g., 5 wt% to 30 wt%, e.g., 5 wt% to 20 wt%, e.g., 5 wt% to 15 wt%, e.g., 5 wt% to 10 wt%, e.g., 10 wt% to 40 wt%, e.g., 10 wt% to 10 wt%, e.g., 10 wt% to 10 wt%, e.g., 10 wt% to 40 wt%, e.g., based on the total weight of the first-stage ethylene-based unsaturated monomer composition. It may be present in the first stage ethylene-based unsaturated monomer composition in an amount of 10% to 30% by weight, for example, 10% to 20% by weight, for example, 10% to 15% by weight.

[0144] The first-stage ethylene-based unsaturated monomer composition may optionally comprise a monomer comprising two or more ethylene-based unsaturated groups per molecule. A monomer comprising two or more ethylene-based unsaturated groups per molecule may comprise a monomer having two ethylene-based unsaturated groups per molecule. Examples of suitable monomers having two ethylene-based 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 ethylene-based 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. Monomers having two or more ethylene-based unsaturated groups per molecule may be present in the first-stage ethylene-based unsaturated monomer composition in an amount of at least 0.1 weight%, e.g., at least 1 weight%, e.g., at least 3 weight%, e.g., at least 5 weight% based on the total weight of the first-stage ethylene-based unsaturated monomer composition. A monomer comprising two or more ethylene-based unsaturated groups per molecule may be present in the first-stage ethylene-based unsaturated monomer composition in an amount of 10% by weight or less, e.g., 5% by weight or less, e.g., 3% by weight or less, based on the total weight of the first-stage ethylene-based unsaturated monomer composition. A monomer comprising two or more ethylene-based unsaturated groups per molecule may be present in an amount of 0.1% to 10% by weight, e.g., 0.1% to 5% by weight, e.g., 0.It may be present in the first-stage ethylene-based unsaturated monomer composition in an amount of 1% to 3% by weight, e.g., 1% to 10% by weight, e.g., 1% to 5% by weight, e.g., 1% to 3% by weight, e.g., 3% to 10% by weight, e.g., 3% to 5% by weight, e.g., 5% to 10% by weight. The use of a monomer comprising two or more ethylene-based unsaturated groups per molecule in the first-stage ethylene-based unsaturated monomer composition may produce a polymeric dispersant comprising ethylene-based unsaturated groups. Accordingly, the polymeric dispersant may comprise ethylene-based unsaturated groups.

[0145] The first-stage ethylene-based unsaturated monomer composition may comprise a first-stage (meth)acrylamide monomer. With respect to the monomer, e.g., (meth)acrylamide monomer, the term "first stage" as used herein is intended to refer to the monomer used during the polymerization of the polymeric dispersant, and the resulting polymeric dispersant comprises residues thereof. The terms "(meth)acrylamide" and similar terms as used herein include both acrylamide and methacrylamide. The first-stage (meth)acrylamide monomer may comprise any suitable (meth)acrylamide monomer, such as, for example, (meth)acrylamide, substituted or unsubstituted monoalkyl (meth)acrylamide monomer, or substituted or unsubstituted dialkyl (meth)acrylamide monomer. Non-limiting examples of the first-stage (meth)acrylamide monomer include (meth)acrylamide, C1-C 18 Includes alkyl (meth)acrylamide monomers, hydroxyl-functional (meth)acrylamide monomers, etc.

[0146] The first step (meth)acrylamide monomer of the first step ethylene-based unsaturated monomer composition is optionally C1-C 18 It may include alkyl (meth)acrylamide monomers. Suitable C1-C 18Examples of alkyl (meth)acrylamide monomers include, but are not limited to, methyl (meth)acrylamide, ethyl (meth)acrylamide, butyl (meth)acrylamide, hexyl (meth)acrylamide, octyl (meth)acrylamide, isodecyl (meth)acrylamide, stearyl (meth)acrylamide, 2-ethylhexyl (meth)acrylamide, isobornyl (meth)acrylamide, t-butyl (meth)acrylamide, etc. C1-C 18 The alkyl (meth)acrylamide monomer may be present in the first-stage ethylene-based unsaturated monomer composition in an amount of at least 30 wt%, e.g., at least 40 wt%, e.g., at least 50 wt%, e.g., at least 60 wt%, e.g., at least 70 wt%, based on the total weight of the first-stage ethylene-based unsaturated monomer composition. C1-C 18 The alkyl (meth)acrylamide monomer may be present in the first-stage ethylene-based unsaturated monomer composition in an amount of 90 weight% or less, e.g., 80 weight% or less, e.g., 70 weight% or less, e.g., 60 weight% or less, based on the total weight of the first-stage ethylene-based unsaturated monomer composition. C1-C 18The alkyl (meth)acrylamide monomer is 30 wt% to 90 wt%, e.g., 30 wt% to 80 wt%, e.g., 30 wt% to 70 wt%, e.g., 30 wt% to 60 wt%, e.g., 40 wt% to 90 wt%, e.g., 40 wt% to 80 wt%, e.g., 40 wt% to 70 wt%, e.g., 40 wt% to 60 wt%, e.g., 50 wt% to 90 wt%, e.g., 50 wt% to 80 wt%, e.g., 50 wt% to 70 wt%, e.g., 50 wt% to 60 wt%, e.g., 60 wt% to 90 wt%, e.g., 60 wt% to 80 wt%, e.g., 60 wt% to 70 wt%, e.g., 70 wt% It may be present in the first stage ethylene-based unsaturated monomer composition in an amount of up to 90 weight%, for example, 70 weight% to 80 weight%.

[0147] The ethylene-based unsaturated monomer composition may optionally include a first-stage hydroxyl-functional (meth)acrylamide monomer. As used herein, the term "hydroxyl-functional (meth)acrylamide" collectively refers to both acrylamide and methacrylamide having a hydroxyl functional group, i.e., having at least one hydroxyl functional group in the molecule. The first-stage hydroxyl-functional (meth)acrylamide monomer includes, for example, hydroxyalkyl (meth)acrylamides such as hydroxymethyl (meth)acrylamide, hydroxyethyl (meth)acrylamide, hydroxypropyl (meth)acrylamide, 2-hydroxypropyl (meth)acrylamide, hydroxybutyl (meth)acrylamide, hydroxypentyl (meth)acrylamide, as well as combinations thereof. The first stage hydroxyl-functional (meth)acrylamide monomer may be present in the first stage ethylene-based unsaturated monomer composition in an amount of at least 1% by weight, e.g., at least 5% by weight, e.g., at least 10% by weight, based on the total weight of the first stage ethylene-based unsaturated monomer composition. The first stage hydroxyl-functional (meth)acrylamide monomer may be present in the first stage ethylene-based unsaturated monomer composition in an amount of 40% by weight or less, e.g., 30% by weight or less, e.g., 25% by weight or less, e.g., 15% by weight or less, based on the total weight of the first stage ethylene-based unsaturated monomer composition.The first stage hydroxyl functional (meth)acrylamide monomer may be present in the first stage ethylene-based unsaturated monomer composition in an amount of 1% to 40% by weight, e.g., 1% to 30% by weight, e.g., 1% to 25% by weight, e.g., 1% to 15% by weight, e.g., 5% to 40% by weight, e.g., 5% to 30% by weight, e.g., 5% to 25% by weight, e.g., 5% to 15% by weight, e.g., 10% to 40% by weight, e.g., 10% to 30% by weight, e.g., 10% to 25% by weight, e.g., 10% to 15% by weight, based on the total weight of the first stage ethylene-based unsaturated monomer composition.

[0148] The first step ethylene-based unsaturated monomer composition may include, be essentially composed of, or be composed of an epoxide-functional ethylene-based unsaturated monomer, and optionally an amino-functional unsaturated monomer, C1-C 18 It may further comprise, or be essentially composed of, or be composed of at least one of alkyl (meth)acrylates, hydroxyl functional (meth)acrylates, vinyl aromatic compounds, and monomers comprising two or more ethylenically unsaturated groups per molecule. Accordingly, the polymeric dispersant may comprise, or be essentially composed of, or be composed of residues of epoxide-functional ethylenically unsaturated monomers, amino-functional unsaturated monomers, C1-C 18The polymeric dispersant may optionally further comprise, essentially consist of, or consist of at least one residue among alkyl (meth)acrylates, hydroxyl functional (meth)acrylates, vinyl aromatic compounds, epoxide functional ethylene-based unsaturated monomers and / or monomers comprising two or more ethylene-based unsaturated groups per molecule. The polymeric dispersant may further comprise any amine incorporated into the polymeric dispersant through reaction with the epoxide functional group.

[0149] The first-stage ethylene-based unsaturated monomer composition may include, be essentially composed of, or be composed of an amino-functional unsaturated monomer, and C1-C 18 The polymeric dispersant may further comprise, essentially constitute, or be composed of at least one of alkyl (meth)acrylates, hydroxyl functional (meth)acrylates, vinyl aromatic compounds, epoxide functional ethylene-based unsaturated monomers, and / or monomers comprising two or more ethylene-based unsaturated groups per molecule. Accordingly, the polymeric dispersant may comprise, essentially constitute, or be composed of residues of amino functional unsaturated monomers and C1-C 18 The polymeric dispersant may further comprise, essentially consist of, or consist of at least one residue among alkyl (meth)acrylates, hydroxyl functional (meth)acrylates, vinyl aromatic compounds, epoxide functional ethylene-based unsaturated monomers and / or monomers comprising two or more ethylene-based unsaturated groups per molecule. The polymeric dispersant may further comprise any amine incorporated into the polymeric dispersant through reaction with the epoxide functional group (if present).

[0150] The first-step ethylene-based unsaturated monomer composition may include, be essentially composed of, or be composed of an acid-functional ethylene-based unsaturated monomer, and optionally C1-C 18It may further comprise, essentially constitute, or be composed of at least one of alkyl (meth)acrylates, hydroxyl functional (meth)acrylates, vinyl aromatic compounds, and / or monomers comprising two or more ethylenically unsaturated groups per molecule. Accordingly, the polymeric dispersant may comprise, essentially constitute, or be composed of residues of acid-functional ethylenically unsaturated monomers, and optionally C1-C 18 It may optionally further include or be essentially composed of at least one residue among alkyl (meth)acrylates, hydroxyl functional (meth)acrylates, vinyl aromatic compounds, acid functional ethylene-based unsaturated monomers and / or monomers comprising two or more ethylene-based unsaturated groups per molecule.

[0151] Polymeric dispersants can be prepared in organic solutions by techniques well known in the art. For example, polymeric dispersants can be prepared by a conventional free radical-initiated solution polymerization technique, wherein a first-stage ethylene-based unsaturated monomer composition is dissolved in a solvent or a mixture of solvents and polymerized in the presence of a free radical initiator. Examples of suitable solvents that can be used for organic solution polymerization include alcohols, e.g., ethanol, tertiary butanol, and tertiary amyl alcohol; ketones, e.g., acetone, methyl ethyl ketone; and ethers, e.g., dimethyl ether of ethylene glycol. Examples of suitable free radical initiators include those soluble in a mixture of monomers, such as azobis-isobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), azobis-(alpha,gamma-dimethylvaleronitrile), tertiary-butyl perbenzoate, tertiary-butyl peracetate, benzoyl peroxide, and ditertiary-butyl peroxide. The free radical initiator may be present in an amount of 0.01 wt% to 6 wt%, e.g., 1.0 wt% to 4.0 wt%, e.g., 2.0 wt% to 3.5 wt% based on the total weight of the first-stage ethylene-based unsaturated monomer composition. In the example, the solvent may first be heated and refluxed, and the mixture of the first-stage ethylene-based unsaturated monomer composition and the free radical initiator may be slowly added to the refluxed solvent. The reaction mixture may be maintained at a polymerization temperature to reduce the free monomer content to less than 1.0 weight%, e.g., less than 0.5 weight%, based on the total weight of the first-stage ethylene-based unsaturated monomer composition.

[0152] Chain transfer agents can be used in the synthesis of polymeric dispersants that are soluble in mixtures of monomers. Suitable, non-limiting examples of such agents include alkyl mercaptans, e.g., tertiary dodecyl mercaptans; ketones, e.g., methyl ethyl ketone; and chlorinated hydrocarbons, e.g., chloroform.

[0153] Polymeric dispersants have a z-average molecular weight (M z ) may be at least 200,000 g / mol, e.g., at least 250,000 g / mol, e.g., at least 300,000 g / mol, and may be 2,000,000 g / mol or less, e.g., 1,200,000 g / mol or less, e.g., 900,000 g / mol or less. The polymeric dispersant has a z-average molecular weight (M z ) can be 200,000 g / mol to 2,000,000 g / mol, e.g., 200,000 g / mol to 1,200,000 g / mol, e.g., 200,000 g / mol to 900,000 g / mol, e.g., 250,000 g / mol to 2,000,000 g / mol, e.g., 250,000 g / mol to 1,200,000 g / mol, e.g., 250,000 g / mol to 900,000 g / mol, e.g., 300,000 to 2,000,000 g / mol, e.g., 300,000 g / mol to 1,200,000 g / mol, e.g., 300,000 g / mol to 900,000 g / mol there is.

[0154] The polymeric dispersant may have a weight average molecular weight of 150,000 g / mol to 750,000 g / mol, e.g., 150,000 g / mol to 400,000 g / mol, e.g., 150,000 g / mol to 300,000 g / mol, e.g., 175,000 g / mol to 750,000 g / mol, e.g., 175,000 g / mol to 400,000 g / mol, e.g., 175,000 g / mol to 300,000 g / mol, e.g., 200,000 g / mol to 750,000 g / mol, e.g., 200,000 g / mol to 400,000 g / mol, e.g., 200,000 g / mol to 300,000 g / mol.

[0155] Ionic groups in a polymeric dispersant can be formed by using an acid or a base to at least partially neutralize basic or acidic groups present in the polymeric dispersant. Ionic groups in the polymeric molecule can be charged neutralized by a counterion. The ionic groups and the charge-neutralizing counterion together form a base group, so that the polymeric dispersant may include a polymeric dispersant containing an ionic base.

[0156] Accordingly, the polymeric dispersant may be at least partially neutralized by treating, for example, with an acid before or during dispersion in a dispersion medium containing water to form a water-dispersible polymeric dispersant containing a cationic base. As used herein, the term "polymeric dispersant containing a cationic base" refers to a polymeric dispersant containing at least partially neutralized cationic functional groups that impart a positive charge, for example, sulfonium and ammonium groups. Non-limiting examples of suitable acids are, in particular, inorganic acids, such as phosphoric acid and sulfamic acid, as well as organic acids, such as acetic acid and lactic acid. In addition to acids, salts, such as dimethylhydroxyethylammonium dihydrogen phosphate and ammonium dihydrogen phosphate, may be used to at least partially neutralize the polymeric dispersant. The polymeric dispersant may be neutralized to an extent of at least 50%, for example, at least 70% of the total theoretical neutralization equivalent. As used herein, “total theoretical neutralization equivalent” refers to the percentage of the stoichiometric amount of acid relative to the total amount of basic groups theoretically present in the polymer. As discussed above, amines may be incorporated into the cationic polymeric dispersant by the reaction of the amine with the epoxide functional groups present in the polymeric dispersant. The dispersion step may be achieved by combining a neutralized or partially neutralized cationic base-containing polymeric dispersant with a dispersion medium of the dispersing phase. Additionally, neutralization and dispersion may be achieved in a single step by combining the polymeric dispersant and the dispersion medium. The polymeric dispersant (or its salt) may be added to the dispersion medium, or the dispersion medium may be added to the polymeric dispersant (or its salt). The pH of the dispersion may be within the range of 5 to 9.

[0157] The cationic base-containing polymeric dispersant may contain a cationic base content sufficient to stabilize the subsequent polymerization of the second-stage ethylene-based unsaturated monomer composition (described below) and to provide a stable resulting addition polymer in the cationic electrodepositable coating composition. Additionally, when the cationic base-containing polymeric dispersant is used with other film-forming resins in the cationic electrodepositable coating composition, it may have a cationic base content sufficient for the composition to be deposited as a coating on a substrate under electrodeposition conditions. The cationic base-containing polymeric dispersant may contain, for example, 0.1 to 5.0, or for example, 0.3 to 1.1 milliequivalents of cationic base per gram of the cationic base-containing polymeric dispersant.

[0158] A polymeric dispersant may be at least partially neutralized by being treated with, for example, a base before or during dispersion in a dispersion medium containing water to form a water-dispersible anionic base-containing polymeric dispersant. As used herein, the term "anionic base-containing polymeric dispersant" refers to an anionic polymeric dispersant comprising at least partially neutralized anionic functional groups that impart a negative charge, for example, carboxylic acids and phosphoric acids. Non-limiting examples of suitable bases are amines, 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 polymeric dispersant may be neutralized to an extent of at least 50 percent of the total theoretical neutralization equivalent, or in some cases, at least 70 percent, or in other cases, 100 percent or more. The dispersion step can be achieved by combining a neutralized or partially neutralized anionic base-containing polymeric dispersant with a dispersion medium of the dispersion phase. Neutralization and dispersion can be achieved in a single step by combining the polymeric dispersant and the dispersion medium. The polymeric dispersant (or its salt) may be added to the dispersion medium, or the dispersion medium may be added to the polymeric dispersant (or its salt). The pH of the dispersion may be within the range of 5 to 9.

[0159] The anionic base-containing polymeric dispersant may contain an anionic base content sufficient to stabilize the subsequent polymerization of the second-stage ethylene-based unsaturated monomer composition (described below) and to provide a stable resulting addition polymer in the anionic electrodepositable coating composition. Additionally, when used with other film-forming resins in the anionic electrodepositable coating composition, the anionic base-containing polymeric dispersant may have an anionic base content sufficient for the composition to be deposited as a coating on a substrate under anionic electrodeposition conditions. The anionic base-containing polymeric dispersant may contain 0.1 to 5.0, for example, 0.3 to 1.1 milliequivalents of anionic base per gram of the anionic base-containing polymeric dispersant.

[0160] The second-stage ethylene-based unsaturated monomer composition comprises a monomer containing three or more ethylene-based unsaturated groups per molecule and C1-C 18 At least one other monomer comprising alkyl (meth)acrylates, hydroxyl functional (meth)acrylates, vinyl aromatic compounds, or any combination thereof, is included, essentially composed of, or composed of. The second-stage ethylene-based unsaturated monomer composition may be substantially free of diene monomers, or in some cases, completely free of them. As used herein, where the second-stage ethylene-based unsaturated monomer composition is described as being "substantially free" of diene monomers, this means that the diene monomers, if present, are present in the monomer composition in an amount of less than 10 weight percent, e.g., less than 5 weight percent, less than 2 weight percent, or in some cases, less than 1 weight percent or 0.1 weight percent, based on the total weight of the second-stage ethylene-based unsaturated monomer composition.

[0161] Non-limiting examples of monomers comprising three or more ethylene-based unsaturated groups per molecule include, for example, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, di-pentaerythritol triacrylate, di-pentaerythritol pentaacrylate, ethoxylated trimethylolpropane triacrylate having 0 to 20 ethoxy units, and ethoxylated trimethylolpropane trimethacrylate having 0 to 20 ethoxy units. The ethylene-based unsaturated monomer(s) having three or more unsaturated sites are used in an amount of 0.1% to 10% by weight, e.g., 0.1% to 5% by weight, based on the total weight of the second-stage ethylene-based unsaturated monomer composition.

[0162] The second stage ethylene-based unsaturated monomer composition is C1-C 18 If present, the alkyl (meth)acrylate may be included in an amount of 20% to 80% by weight, for example, 20% to 60% by weight, based on the total weight of the second-stage ethylene-based unsaturated monomer composition.

[0163] The second stage ethylene-based unsaturated monomer composition may contain a hydroxyl-functional (meth)acrylate, if present, in an amount of 5% to 20% by weight, for example, 5% to 15% by weight, based on the total weight of the second stage ethylene-based unsaturated monomer composition.

[0164] The second stage ethylene-based unsaturated monomer composition may contain a vinyl aromatic compound, if present, in an amount of 20% to 80% by weight, for example, 20% to 60% by weight, based on the total weight of the second stage ethylene-based unsaturated monomer composition.

[0165] The second-stage ethylene-based unsaturated monomer composition comprises, is essentially composed of, or is composed of one or more second-stage (meth)acrylamide monomers. The term “second stage” as used herein with respect to monomers, e.g., (meth)acrylamide monomers, is intended to refer to monomers used during the second polymerization step of an addition polymer polymerized in the presence of a pre-formed polymeric dispersant, and the resulting addition polymer comprises residues thereof. The (meth)acrylamide monomer may comprise any suitable (meth)acrylamide monomer, such as, e.g., (meth)acrylamide, substituted or unsubstituted monoalkyl (meth)acrylamide, or substituted or unsubstituted dialkyl (meth)acrylamide. Non-limiting examples include (meth)acrylamide, C1-C 18 Includes alkyl (meth)acrylamide, hydroxyl-functional (meth)acrylamide, etc.

[0166] The second stage ethylene-based unsaturated monomer composition may include (meth)acrylamide, e.g., (meth)acrylamide or acrylamide, or may be essentially composed of or composed of such. The (meth)acrylamide monomer may be present in the second stage ethylene-based unsaturated monomer composition in an amount of at least 20 wt%, e.g., at least 30 wt%, e.g., at least 40 wt%, e.g., at least 50 wt%, e.g., at least 60 wt%, e.g., at least 70 wt%, e.g., at least 80 wt%, e.g., at least 90 wt%, e.g., at least 95 wt%, e.g., at least 99 wt%, e.g., 100 wt% based on the total weight of the second stage ethylene-based unsaturated monomer composition. The (meth)acrylamide monomer may be present in the second-stage ethylene-based unsaturated monomer composition in an amount of 99% by weight or less, e.g., 90% by weight or less, e.g., 80% by weight or less, e.g., 70% by weight or less, e.g., 60% by weight or less, e.g., 50% by weight or less, based on the total weight of the second-stage ethylene-based unsaturated monomer composition. The (meth)acrylamide monomer is 20 wt% to 100 wt%, e.g., 20 wt% to 99 wt%, e.g., 20 wt% to 90 wt%, e.g., 20 wt% to 80 wt%, e.g., 20 wt% to 70 wt%, e.g., 20 wt% to 60 wt%, e.g., 20 wt% to 50 wt%, e.g., 30 wt% to 100 wt%, e.g., 30 wt% to 99 wt%, e.g., 30 wt% to 90 wt%, e.g., 30 wt% to 80 wt%, e.g., 30 wt% to 70 wt%, e.g., 30 wt% to 60 wt%, e.g., 30 wt% to 50 wt%, e.g., 40 wt% to 100 wt%, e.g., 40 wt% to 40 wt%. weight% to 99 weight%, e.g., 40 weight% to 90 weight%,For example, 40 wt% to 80 wt%, for example, 40 wt% to 70 wt%, for example, 40 wt% to 60 wt%, for example, 40 wt% to 50 wt%, for example, 50 wt% to 100 wt%, for example, 50 wt% to 99 wt%, for example, 50 wt% to 90 wt%, for example, 50 wt% to 80 wt%, for example, 50 wt% to 70 wt%, for example, 50 wt% to 60 wt%, for example, 60 wt% to 100 wt%, for example, 60 wt% to 99 wt%, for example, 60 wt% to 90 wt%, for example, 60 wt% to 80 wt%, for example, 60 wt% to 70 wt%, for example, 70 wt% to 100 wt%, for example, 70 wt% to 99 wt%, for example, 70 It may be present in the second-stage ethylene-based unsaturated monomer composition in an amount of 90% to 90% by weight, e.g., 70% to 80% by weight, e.g., 80% to 100% by weight, e.g., 80% to 99% by weight, e.g., 80% to 90% by weight, e.g., 90% to 100% by weight, e.g., 90% to 99% by weight, e.g., 95% to 100% by weight, e.g., 95% to 99% by weight, e.g., 95% to 100% by weight, e.g., 95% to 100% by weight, e.g., 95% to 99% by weight.

[0167] The second-stage ethylene-based unsaturated monomer composition may include, be essentially composed of, or be composed of a second-stage hydroxyl-functional (meth)acrylamide monomer. The second-stage hydroxyl-functional (meth)acrylamide monomer may include a primary hydroxyl group. The second-stage hydroxyl-functional (meth)acrylamide monomer may include a secondary hydroxyl group. The second step hydroxyl-functional (meth)acrylamide monomer may include one or more of C1-C9 hydroxyalkyl (meth)acrylamide, e.g., C1-C6 hydroxyalkyl (meth)acrylamide, e.g., C1-C5 hydroxyalkyl (meth)acrylamide, e.g., hydroxymethyl (meth)acrylamide, hydroxyethyl (meth)acrylamide, hydroxypropyl (meth)acrylamide, 2-hydroxypropyl (meth)acrylamide, hydroxybutyl (meth)acrylamide, hydroxypentyl (meth)acrylamide, or combinations thereof.

[0168] The second stage hydroxyl functional (meth)acrylamide monomer may be present in the second stage ethylene-based unsaturated monomer composition in an amount of at least 20 wt%, e.g., at least 30 wt%, e.g., at least 40 wt%, e.g., at least 50 wt%, e.g., at least 60 wt%, e.g., at least 70 wt%, e.g., at least 80 wt%, e.g., at least 90 wt%, e.g., at least 95 wt%, e.g., at least 99 wt%, e.g., 100 wt% based on the total weight of the second stage ethylene-based unsaturated monomer composition. The second stage hydroxyl-functional (meth)acrylamide monomer may be present in the second stage ethylene-based unsaturated monomer composition in an amount of 99% by weight or less, e.g., 90% by weight or less, e.g., 80% by weight or less, e.g., 70% by weight or less, e.g., 60% by weight or less, e.g., 50% by weight or less, based on the total weight of the second stage ethylene-based unsaturated monomer composition. The second-stage hydroxyl-functional (meth)acrylamide monomer is 20 wt% to 100 wt%, e.g., 20 wt% to 99 wt%, e.g., 20 wt% to 90 wt%, e.g., 20 wt% to 80 wt%, e.g., 20 wt% to 70 wt%, e.g., 20 wt% to 60 wt%, e.g., 20 wt% to 50 wt%, e.g., 30 wt% to 100 wt%, e.g., 30 wt% to 99 wt%, e.g., 30 wt% to 90 wt%, e.g., 30 wt% to 80 wt%, e.g., 30 wt% to 70 wt%, e.g., 30 wt% to 60 wt%, e.g., 30 wt% to 50 wt%, e.g., 40 wt% to 100 wt% based on the total weight of the second-stage ethylene-based unsaturated monomer composition. weight%, e.g., 40 weight% to 99 weight%, e.g., 40 weight% to 90 weight%, e.g., 40 weight% to 80 weight%, e.g., 40 weight% to 70 weight%, e.g.,40 wt% to 60 wt%, e.g., 40 wt% to 50 wt%, e.g., 50 wt% to 100 wt%, e.g., 50 wt% to 99 wt%, e.g., 50 wt% to 90 wt%, e.g., 50 wt% to 80 wt%, e.g., 50 wt% to 70 wt%, e.g., 50 wt% to 60 wt%, e.g., 60 wt% to 100 wt%, e.g., 60 wt% to 99 wt%, e.g., 60 wt% to 90 wt%, e.g., 60 wt% to 80 wt%, e.g., 60 wt% to 70 wt%, e.g., 70 wt% to 100 wt%, e.g., 70 wt% to 99 wt%, e.g., 70 wt% to 90 wt%, e.g., 70 wt% to 80 wt%, e.g., 80 wt% It may be present in the second-stage ethylene-based unsaturated monomer composition in an amount of up to 100 wt%, e.g., 80 wt% to 99 wt%, e.g., 80 wt% to 90 wt%, e.g., 90 wt% to 100 wt%, e.g., 90 wt% to 99 wt%, e.g., 95 wt% to 100 wt%, e.g., 95 wt% to 99 wt%, e.g., 95 wt% to 100 wt%, e.g., 95 wt% to 99 wt%.

[0169] The second-stage ethylene-based unsaturated monomer composition may optionally further comprise a phospho-functional ethylene-based unsaturated monomer. The phospho-functional group may comprise a phosphonic acid group, a phosphinic acid group, or a combination thereof and salts thereof. The phospho-functional ethylene-based unsaturated monomer may be a phosphate ester of an alcohol containing or substituted with a polymerizable vinyl group or an olefin group. Suitable phospho-functional ethylene-based unsaturated monomers are phosphoalkyl (meth)acrylates, e.g., phosphoethyl (meth)acrylate, phosphopropyl (meth)acrylate, phosphobutyl (meth)acrylate, salts of phosphoalkyl (meth)acrylates, and mixtures thereof; or CH3 and R p =alkyl and n is 1 to 20 ―C(O)―O―(R p O) n—P(O)(OH)2, e.g., SIPOMER PAM-100, SIPOMER PAM-200, SIPOMER PAM-300 and SIPOMER PAM-4000 (all available from Solvay); phosphoalkoxy (meth)acrylates, e.g., phosphoethylene glycol (meth)acrylate, phosphodi-ethylene glycol (meth)acrylate, phosphotri-ethylene glycol (meth)acrylate, phosphopropylene glycol (meth)acrylate, phosphodipropylene glycol (meth)acrylate, phosphotri-propylene glycol (meth)acrylate, salts thereof and mixtures thereof may be included. The phosphite-functional ethylene-based unsaturated monomer may be present in the second-stage ethylene-based unsaturated monomer composition in an amount of at least 0.1% by weight, e.g., at least 0.5% by weight, e.g., at least 1% by weight, e.g., at least 1.5% by weight, based on the total weight of the second-stage ethylene-based unsaturated monomer composition. The phosphite-functional ethylene-based unsaturated monomer may be present in the second-stage ethylene-based unsaturated monomer composition in an amount of 20% by weight or less, e.g., 10% by weight or less, e.g., 4% by weight or less, e.g., 2.5% by weight or less, based on the total weight of the second-stage ethylene-based unsaturated monomer composition. The phosphite-functional ethylene-based unsaturated monomer is present in an amount of 0.1% to 20% by weight, e.g., 0.1% to 10% by weight, e.g., 0.1% to 4% by weight, e.g., 0.1% to 2.5% by weight, e.g., 0.5% to 20% by weight, e.g., 0.5% to 10% by weight, e.g., 0.5% to 4% by weight, e.g., 0.5% to 2.5% by weight, e.g., 1% to 20% by weight, e.g., 1% to 10% by weight, e.g., 1% to 4% by weight, e.g., 1% to 2.5% by weight, e.g., 1.It may be present in the second stage ethylene-based unsaturated monomer composition in an amount of 5% to 20% by weight, for example, 1.5% to 10% by weight, for example, 1.5% to 4% by weight, for example, 1.5% to 2.5% by weight.

[0170] The second-stage ethylene-based unsaturated monomer composition may optionally include other ethylene-based unsaturated monomers. The other ethylene-based unsaturated monomers may include any ethylene-based unsaturated monomers known in the art. Examples of other ethylene-based unsaturated monomers that may be used in the second-stage ethylene-based unsaturated monomer composition include, but are not limited to, di(methyl)acrylates and poly(ethylene glycol) (meth)acrylates, as well as the monomers described above in connection with the manufacture of polymeric dispersants.If present, these monomers are present in an amount of 1 wt% to 80 wt%, e.g., 1 wt% to 70 wt%, e.g., 1 wt% to 60 wt%, e.g., 1 wt% to 50 wt%, e.g., 1 wt% to 40 wt%, e.g., 1 wt% to 30 wt%, e.g., 1 wt% to 20 wt%, e.g., 1 wt% to 10 wt%, e.g., 1 wt% to 5 wt%, e.g., 5 wt% to 80 wt%, e.g., 5 wt% to 70 wt%, e.g., 5 wt% to 60 wt%, e.g., 5 wt% to 50 wt%, e.g., 5 wt% to 40 wt%, e.g., 5 wt% to 30 wt%, e.g., 5 wt% to 20 wt%, e.g., 5 wt% to 10 wt%, e.g., based on the total weight of the second-stage ethylene-based unsaturated monomer composition. 10 wt% to 80 wt%, e.g., 10 wt% to 70 wt%, e.g., 10 wt% to 60 wt%, e.g., 10 wt% to 50 wt%, e.g., 10 wt% to 40 wt%, e.g., 10 wt% to 30 wt%, e.g., 10 wt% to 20 wt%, e.g., 20 wt% to 80 wt%, e.g., 20 wt% to 70 wt%, e.g., 20 wt% to 60 wt%, e.g., 20 wt% to 50 wt%, e.g., 20 wt% to 40 wt%, e.g., 20 wt% to 30 wt%, e.g., 30 wt% to 80 wt%, e.g., 30 wt% to 70 wt%, e.g., 30 wt% to 60 wt%, e.g., 30 wt% to 50 wt%, e.g., 30 wt% to It may be present in an amount of 40 weight%.

[0171] The addition polymer may comprise a polymerization product comprising a residue of a polymeric dispersant of 10 wt%, e.g., at least 20 wt%, e.g., at least 30 wt%, e.g., at least 40 wt%, e.g., at least 50 wt%, e.g., at least 60 wt%, e.g., at least 70 wt%, e.g., at least 80 wt%, e.g., 90 wt% or less, e.g., 80 wt% or less, e.g., 70 wt% or less, e.g., 60 wt% or less, e.g., 50 wt% or less, e.g., 40 wt% or less, e.g., 30 wt% or less, e.g., 2The addition polymer is 10 wt% to 90 wt%, e.g., 10 wt% to 80 wt%, e.g., 10 wt% to 70 wt%, e.g., 10 wt% to 60 wt%, e.g., 10 wt% to 50 wt%, e.g., 10 wt% to 40 wt%, e.g., 10 wt% to 30 wt%, e.g., 10 wt% to 20 wt%, e.g., 20 wt% to 90 wt%, e.g., 20 wt% to 80 wt%, e.g., 20 wt% to 70 wt%, e.g., 20 wt% to 60 wt%, e.g., 20 wt% to 50 wt%, e.g., 20 wt% to 40 wt%, e.g., 20 wt% to 30 wt%, e.g., 30 wt% to 90 wt%, e.g., 30 wt% to 80 wt%, e.g., 30 wt% to 70 wt%, e.g., 30 wt% to 60 wt%, e.g., 30 wt% to 50 wt%, e.g., 30 wt% to 40 wt%, e.g., 40 wt% to 90 wt%, e.g., 40 wt% to 80 wt%, e.g., 40 wt% to 70 wt%, e.g., 40 wt% to 60 wt%, e.g., 40 wt% to 50 wt%, e.g., 50 wt% to 90 wt%, e.g., 50 wt% to 80 wt%, e.g., 50 wt% to 70 wt%, e.g., 50 wt% to 60 wt%, e.g., 60 wt% to 90 wt%, e.g., 60 wt% to 80 wt%, e.g., 60 wt% to 70 wt%, e.g., 70 wt% to 90 wt%, e.g., 70 wt% to 80 wt%, For example, it may include a polymerization product containing 80% to 90% by weight of residue of a polymeric dispersant, and the weight percentage is based on the total weight of the addition polymer.

[0172] The addition polymer may comprise a polymerization product comprising at least 10 wt%, e.g., at least 20 wt%, e.g., at least 30 wt%, e.g., at least 40 wt%, e.g., at least 50 wt%, e.g., at least 60 wt%, e.g., at least 70 wt%, e.g., at least 80 wt%, and the weight percentage is based on the total weight of the addition polymer. The addition polymer may comprise a polymerization product comprising at least 90 wt%, e.g., 80 wt%, e.g., 70 wt%, e.g., 60 wt%, e.g., 50 wt%, e.g., 40 wt%, e.g., 30 wt%, e.g., 20 wt%, e.g., 20 wt%, e.g., at least 40 wt%, e.g., 30 wt%, e.g., 20 wt%, e.g., at least 20 wt%, and the weight percentage is based on the total weight of the addition polymer.The addition polymer is 10 wt% to 90 wt%, e.g., 10 wt% to 80 wt%, e.g., 10 wt% to 70 wt%, e.g., 10 wt% to 60 wt%, e.g., 10 wt% to 50 wt%, e.g., 10 wt% to 40 wt%, e.g., 10 wt% to 30 wt%, e.g., 10 wt% to 20 wt%, e.g., 20 wt% to 90 wt%, e.g., 20 wt% to 80 wt%, e.g., 20 wt% to 70 wt%, e.g., 20 wt% to 60 wt%, e.g., 20 wt% to 50 wt%, e.g., 20 wt% to 40 wt%, e.g., 20 wt% to 30 wt%, e.g., 30 wt% to 90 wt%, e.g., 30 wt% to 80 wt%, e.g., 30 wt% to 70 wt%, e.g., 30 wt% to 60 wt%, e.g., 30 wt% to 50 wt%, e.g., 30 wt% to 40 wt%, e.g., 40 wt% to 90 wt%, e.g., 40 wt% to 80 wt%, e.g., 40 wt% to 70 wt%, e.g., 40 wt% to 60 wt%, e.g., 40 wt% to 50 wt%, e.g., 50 wt% to 90 wt%, e.g., 50 wt% to 80 wt%, e.g., 50 wt% to 70 wt%, e.g., 50 wt% to 60 wt%, e.g., 60 wt% to 90 wt%, e.g., 60 wt% to 80 wt%, e.g., 60 wt% to 70 wt%, e.g., 70 wt% to 90 wt%, e.g., 70 wt% to 80 wt%, For example, it may include a polymerization product comprising 80% to 90% by weight of the residue of the second-stage ethylene-based unsaturated monomer composition, and the weight percentage is based on the total weight of the addition polymer.

[0173] The addition polymer may include a polymeric dispersant and a polymerization product of the second-stage ethylene-based unsaturated monomer composition, wherein the weight ratio of the second-stage ethylene-based unsaturated monomer composition to the polymeric dispersant is 9:1 to 1:9, e.g., 9:1 to 1:4, e.g., 9:1 to 3:7, e.g., 9:1 to 2:3, e.g., 9:1 to 1:1, e.g., 9:1 to 3:2, e.g., 9:1 to 7:3, e.g., 9:1 to 4:1, e.g., 4:1 to 1:9, e.g., 4:1 to 1:4, e.g., 4:1 to 3:7, e.g., 4:1 to 2:3, e.g., 4:1 to 1:1, e.g., 4:1 to 3:2, e.g., 4:1 to 7:3, e.g., 4:1 to 9:1, e.g., 7:3 to 1:9, e.g., 7:3 to 1:4, e.g., 7:3 to 3:7, e.g., 7:3 to 2:3, e.g., 7:3 to 1:1, e.g., 7:3 to 3:2, e.g., 7:3 to 4:1, e.g., 7:3 to 9:1, e.g., 3:2 to 1:9, e.g., 3:2 to 1:4, e.g., 3:2 to 3:7, e.g., 3:2 to 2:3, e.g., 3:2 to 1:1, e.g., 3:2 to 7:3, e.g., 3:2 to 4:1, e.g., 3:2 to 9:1, e.g., 1:1 to 1:9, e.g., 1:1 to 1:4, e.g., 1:1 to 3:7, e.g., 1:1 to 2:3, e.g., 1:1 to 3:2, For example, 1:1 to 7:3, for example, 1:1 to 4:1, for example, 1:1 to 9:1, for example, 2:3 to 1:9, for example, 2:3 to 1:4, for example, 2:3 to 3:7, for example, 2:3 to 1:1, for example, 2:3 to 3:2, for example, 9:1 to 7:3, for example, 2:3 to 4:1, for example, 2:3 to 9:1, for example, 3:7 to 1:9, for example, 3:7 to 1:4, for example, 3:7 to 2:3, for example, 3:7 to 1:1, for example, 3:7 to 3:2,For example, it may be 3:7 to 7:3, for example, 3:7 to 4:1, for example, 3:7 to 9:1, for example, 1:4 to 1:9, for example, 1.4 to 3:7, for example, 1.4 to 2:3, for example, 1.4 to 1:1, for example, 1.4 to 3:2, for example, 1.4 to 7:3, for example, 1.4 to 4:1, for example, 1:4 to 9:1, for example, 1:9 to 1:4, for example, 1:9 to 3:7, for example, 1:9 to 2:3, for example, 1:9 to 1:1, for example, 1:9 to 3:2, for example, 1:9 to 7:3, for example, 1:9 to 4:1, for example, 1:9 to 9:1.

[0174] The addition polymer may include a polymeric dispersant and a polymerization product of a second-stage ethylene-based unsaturated monomer composition, and the weight ratio of residues of the second-stage ethylene-based unsaturated monomer composition to residues of the polymeric dispersant is 9:1 to 1:9, e.g., 9:1 to 1:4, e.g., 9:1 to 3:7, e.g., 9:1 to 2:3, e.g., 9:1 to 1:1, e.g., 9:1 to 3:2, e.g., 9:1 to 7:3, e.g., 9:1 to 4:1, e.g., 4:1 to 1:9, e.g., 4:1 to 1:4, e.g., 4:1 to 3:7, e.g., 4:1 to 2:3, e.g., 4:1 to 1:1, e.g., 4:1 to 3:2, e.g., 4:1 to 7:3, e.g., 4:1 to 9:1. For example, 7:3 to 1:9, for example, 7:3 to 1:4, for example, 7:3 to 3:7, for example, 7:3 to 2:3, for example, 7:3 to 1:1, for example, 7:3 to 3:2, for example, 7:3 to 4:1, for example, 7:3 to 9:1, for example, 3:2 to 1:9, for example, 3:2 to 1:4, for example, 3:2 to 3:7, for example, 3:2 to 2:3, for example, 3:2 to 1:1, for example, 3:2 to 7:3, for example, 3:2 to 4:1, for example, 3:2 to 9:1, for example, 1:1 to 1:9, for example, 1:1 to 1:4, for example, 1:1 to 3:7, for example, 1:1 to 2:3, for example, 1:1 to 3:2, e.g., 1:1 to 7:3, e.g., 1:1 to 4:1, e.g., 1:1 to 9:1, e.g., 2:3 to 1:9, e.g., 2:3 to 1:4, e.g., 2:3 to 3:7, e.g., 2:3 to 1:1, e.g., 2:3 to 3:2, e.g., 9:1 to 7:3, e.g., 2:3 to 4:1, e.g., 2:3 to 9:1, e.g., 3:7 to 1:9, e.g., 3:7 to 1:4, e.g., 3:7 to 2:3, e.g., 3:7 to 1:1, e.g.,It may be 3:7 to 3:2, e.g., 3:7 to 7:3, e.g., 3:7 to 4:1, e.g., 3:7 to 9:1, e.g., 1:4 to 1:9, e.g., 1.4 to 3:7, e.g., 1.4 to 2:3, e.g., 1.4 to 1:1, e.g., 1.4 to 3:2, e.g., 1.4 to 7:3, e.g., 1.4 to 4:1, e.g., 1:4 to 9:1, e.g., 1:9 to 1:4, e.g., 1:9 to 3:7, e.g., 1:9 to 2:3, e.g., 1:9 to 1:1, e.g., 1:9 to 3:2, e.g., 1:9 to 7:3, e.g., 1:9 to 4:1, e.g., 1:9 to 9:1.

[0175] The addition polymer may include an active hydrogen functional group. The active hydrogen functional group may include a hydroxyl group, a mercaptan group, a primary amine group and / or a secondary amine group.

[0176] The addition polymer may have a theoretical hydroxyl equivalent of at least 120 g / hydroxyl group ("OH"), e.g., at least 130 g / OH, e.g., at least 140 g / OH, e.g., at least 145 g / OH, or 310 g / OH or less, e.g., 275 g / OH or less, e.g., 200 g / OH or less, e.g., 160 g / OH or less. The addition polymer may have a theoretical hydroxyl equivalent of 120 g / OH to 310 g / OH, e.g., 130 g / OH to 275 g / OH, e.g., 140 g / OH to 200 g / OH, e.g., 145 g / OH to 160 g / OH.

[0177] The addition polymer may have a theoretical hydroxyl value of at least 190 mg KOH / gram addition polymer, e.g., at least 250 mg KOH / gram addition polymer, e.g., at least 320 mg KOH / gram addition polymer, e.g., at least 355 mg KOH / gram addition polymer, or 400 mg KOH / gram addition polymer or less, e.g., 390 mg KOH / gram addition polymer or less, e.g., 380 mg KOH / gram addition polymer or less, e.g., 370 mg KOH / gram addition polymer or less. The addition polymer may have a theoretical hydroxyl value of 190 to 400 mg KOH / gram addition polymer, e.g., 250 to 390 mg KOH / gram addition polymer, e.g., 320 to 380 mg KOH / gram addition polymer, e.g., 355 to 370 mg KOH / gram addition polymer. The term “theoretical hydroxyl value” as used herein refers to the number of milligrams of potassium hydroxide required to neutralize the acetic acid taken upon the acetylation of 1 gram of a chemical containing a free hydroxyl group, and is determined by the theoretical calculation of the number of free hydroxyl groups theoretically present in 1 gram of an addition polymer.

[0178] The addition polymer may have a z-average molecular weight of 500,000 g / mol to 5,000,000 g / mol, e.g., 1,400,000 g / mol to 2,600,000 g / mol, e.g., 1,800,000 g / mol to 2,200,000 g / mol, e.g., 1,500,000 g / mol to 1,700,000 g / mol, e.g., 750,000 g / mol to 950,000 g / mol. The z-average molecular weight can be measured by gel permeation chromatography using a polystyrene standard according to the same procedure as described above.

[0179] The addition polymer may have a weight-average molecular weight of 200,000 g / mol to 1,600,000 g / mol, e.g., 400,000 g / mol to 900,000 g / mol, e.g., 500,000 g / mol to 800,000 g / mol. The weight-average molecular weight can be measured by gel permeation chromatography using a polystyrene standard according to the same procedure as described above.

[0180] The addition polymer may be substantially free of silicon, essentially free of silicon, or completely free of silicon. As used herein, "silicon" refers to elemental silicon or any silicon-containing compound, such as an organosilicon compound including an alkoxysilane. As used herein, the addition polymer is "substantially free of silicon" if silicon is present in an amount of less than 2 weight percent based on the total weight of the addition polymer. As used herein, the addition polymer is "essentially free of silicon" if silicon is present in an amount of less than 1 weight percent based on the total weight of the addition polymer. As used herein, the addition polymer is "completely free of silicon" if silicon is not present in the addition polymer, i.e., 0 weight percent.

[0181] An addition polymer may be formed by a two-step polymerization process. The first step of the two-step polymerization process comprises forming a polymeric dispersant from the first step ethylene-based unsaturated monomer composition as described above. The second step of the two-step polymerization process comprises forming an addition polymer comprising the polymerization product of the polymeric dispersant formed during the first and second step ethylene-based unsaturated monomer compositions as described above. The second step of the polymerization process may comprise: (a) forming an aqueous dispersion by dispersing the second step ethylene-based unsaturated monomer composition and a free radical initiator in a dispersion medium containing water in the presence of at least partially neutralized polymeric dispersant; and (b) forming an aqueous dispersion comprising an addition polymer formed by heating the aqueous dispersion in the presence of the free radical initiator to polymerize the components under emulsion polymerization conditions. The polymerization time and temperature may depend on another selected component, and in some cases, the reaction scale. For example, polymerization can be carried out at 40°C to 100°C for 2 to 20 hours.

[0182] The free radical initiator used for polymerizing the polymeric dispersant and the second-stage ethylene-based unsaturated monomer composition may be selected from any of those used for aqueous addition polymerization techniques, including redox pair initiators, peroxides, hydroperoxides, peroxydicarbonates, azo compounds, etc. The free radical initiator may be present in an amount of 0.01% to 5% by weight, e.g., 0.05% to 2.0% by weight, e.g., 0.1% to 1.5% by weight, based on the weight of the second-stage ethylene-based unsaturated monomer composition. Chain transfer agents soluble in the monomer composition, e.g., alkyl mercaptans, e.g., tertiary-dodecyl mercaptan, 2-mercaptoethanol, isooctyl mercaptopropionate, n-octyl mercaptan, or 3-mercaptoacetic acid, may be used for polymerizing the polymeric dispersant and the second-stage ethylene-based unsaturated monomer composition. Other chain transfer agents, e.g., ketones, e.g., methyl ethyl ketone, and chlorocarbons, e.g., chloroform, may be used. If present, the amount of the chain transfer agent may be 0.1% to 6.0% by weight based on the weight of the second-stage ethylene-based unsaturated monomer composition. Relatively high molecular weight polyfunctional mercaptans may be wholly or partially substituted for the chain transfer agent. These molecules may have a molecular weight range of, for example, 94 to 1,000 g / mol or more. The functionality may be about 2 to about 4. If present, the amount of such multifunctional mercaptan may be 0.1% to 6.0% by weight based on the weight of the second-stage ethylene-based unsaturated monomer composition.

[0183] According to the present disclosure, water may be present in the aqueous dispersion in an amount of at least 40 weight%, e.g., at least 50 weight%, e.g., at least 60 weight%, e.g., at least 75 weight%, based on the total weight of the aqueous dispersion. Water may be present in the aqueous dispersion in an amount of 90 weight% or less, e.g., 75 weight% or less, e.g., 60 weight% or less, based on the total weight of the aqueous dispersion. Water may be present in the aqueous dispersion in an amount of 40% to 90% by weight, e.g., 40% to 75% by weight, e.g., 40% to 60% by weight, e.g., 50% to 90% by weight, e.g., 50% to 75% by weight, e.g., 50% to 60% by weight, e.g., 60% to 90% by weight, e.g., 60% to 75% by weight, e.g., 75% to 90% by weight, based on the total weight of the aqueous dispersion. The addition polymer may be added to other components of the electrodepositable coating composition as an aqueous dispersion of the addition polymer.

[0184] The dispersion medium may further comprise an organic cosolvent in addition to water. The organic cosolvent 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 an alkyl group, such as monoethyl and monobutyl ethers of these glycols. Other examples of at least partially water-miscible solvents include alcohols, such as ethanol, isopropanol, butanol, and diacetone alcohol. When used, the organic cosolvent may be present in an amount of less than 10 weight percent, for example, less than 5 weight percent, based on the total weight of the dispersion medium.

[0185] The addition polymer described above may be present in the electrodeposited coating composition in an amount of at least 0.01 wt%, e.g., at least 0.1 wt%, e.g., at least 0.3 wt%, e.g., at least 0.5 wt%, e.g., at least 0.75 wt%, e.g., 1 wt%, based on the total weight of the resin solid of the electrodeposited coating composition. The addition polymer described above may be present in the electrodeposited coating composition in an amount of 5 wt% or less, e.g., 3 wt% or less, e.g., 2 wt% or less, e.g., 1.5 wt% or less, e.g., 1 wt% or less, e.g., 0.75 wt% or less, based on the total weight of the resin solid of the electrodeposited coating composition. The addition polymer described above is present in an amount of 0.01 wt% to 5 wt%, e.g., 0.01 wt% to 3 wt%, e.g., 0.01 wt% to 2 wt%, e.g., 0.01 wt% to 1.5 wt%, e.g., 0.01 wt% to 1 wt%, e.g., 0.01 wt% to 0.75 wt%, e.g., 0.1 wt% to 5 wt%, e.g., 0.1 wt% to 3 wt%, e.g., 0.1 wt% to 2 wt%, e.g., 0.1 wt% to 1.5 wt%, e.g., 0.1 wt% to 1 wt%, e.g., 0.1 wt% to 0.75 wt%, e.g., 0.3 wt% to 5 wt%, e.g., 0.3 wt% to 3 wt%, e.g., 0.3 wt% to 2 wt%, e.g., based on the total weight of the resin solid of the electrodepositable coating composition. 0.3 wt% to 1.5 wt%, e.g., 0.3 wt% to 1 wt%, e.g., 0.3 wt% to 0.75 wt%, e.g., 0.5 wt% to 5 wt%, e.g., 0.5 wt% to 3 wt%, e.g., 0.5 wt% to 2 wt%, e.g., 0.5 wt% to 1.5 wt%, e.g., 0.5 wt% to 1 wt%, e.g., 0.5 wt% to 0.It may be present in the electrodepositable coating composition in an amount of 75 weight%, for example, 1 weight% to 5 weight%, for example, 1 weight% to 3 weight%, for example, 1 weight% to 2 weight%, for example, 1 weight% to 1.5 weight%.

[0186] Hydroxyl functional addition polymer As explained above, the edge control adduct is a hydroxyl-functional addition polymer comprising constituent units, of which at least 70% is of Formula VIII:

[0187] ―[―C(R 1 )2―C(R 1 )(OH)―]― (VIII),

[0188] Includes and each R 1 is independently one of hydrogen, an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an alkylcycloalkyl group, a substituted alkylcycloalkyl group, a cycloalkylalkyl group, a substituted cycloalkylalkyl group, an aryl group, a substituted aryl group, an alkylaryl group, a substituted alkylaryl group, a cycloalkylaryl group, a substituted cycloalkylaryl group, an arylalkyl group, a substituted arylalkyl group, an arylcycloalkyl group, or a substituted arylcycloalkyl group, and the % comprises a hydroxyl functional addition polymer based on the total constituent unit of the hydroxyl functional addition polymer. The addition polymer described above may include a hydroxyl functional group, but this is different from the hydroxyl functional addition polymer.

[0189] Non-limiting examples of suitable alkyl radicals are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, amyl, hexyl, and 2-ethylhexyl.

[0190] Non-limiting examples of suitable cycloalkyl radicals are cyclobutyl, cyclopentyl, and cyclohexyl.

[0191] Non-limiting examples of suitable alkylcycloalkyl radicals are methylenecyclohexane, ethylenecyclohexane, and propane-1,3-diylcyclohexane.

[0192] Non-limiting examples of suitable cycloalkylalkyl radicals are 2-, 3- and 4-methyl-, -ethyl-, -propyl- and -butylcyclohex-1-yl.

[0193] Non-limiting examples of suitable aryl radicals are phenyl, naphthyl, and biphenylyl.

[0194] Non-limiting examples of suitable alkylaryl radicals are benzyl-[sic], ethylene-, and propane-1,3-diyl-benzene.

[0195] Non-limiting examples of suitable cycloalkylaryl radicals are 2-, 3- and 4-phenylcyclohex-1-yl.

[0196] Non-limiting examples of suitable arylalkyl radicals are 2-, 3- and 4-methyl-, -ethyl-, -propyl- and -butylphen-1-yl.

[0197] Non-limiting examples of suitable arylcycloalkyl radicals are 2-, 3- and 4-cyclohexylphen-1-yl.

[0198] The radical R described above 1 It can be substituted. Electron-recruiting atoms, electron-donating atoms, or organic radicals can be used for this purpose.

[0199] Examples of suitable substituents include halogen atoms, e.g., chlorine or fluorine; nitrile groups, nitro groups; partial or complete halogenation, e.g., chlorination and / or fluorination; alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl and arylcycloalkyl radicals (including those exemplified above), particularly, tertiary-butyl; aryloxy, alkyloxy and cycloalkyloxy radicals, particularly, phenoxy, naphthoxy, methoxy, ethoxy, propoxy, butyloxy or cyclohexyloxy; arylthio, alkylthio and cycloalkylthio radicals, particularly, phenylthio, naphthylthio, methylthio, ethylthio, propylthio, butylthio or cyclohexylthio; hydroxyl groups; and / or primary, secondary and / or tertiary amino groups, particularly amino, N-methylamino, N-ethylamino, N-propylamino, N-phenylamino, N-cyclohexylamino, N,N-dimethylamino, N,N-diethylamino, N,N-dipropylamino, N,N-diphenylamino, N,N-dicyclohexylamino, N-cyclohexyl-N-methylamino or N-ethyl-N-methylamino.

[0200] R 1 It may contain hydrogen, be essentially composed of it, or be composed of it. For example, R 1 It may contain hydrogen in at least 80%, for example, at least 90%, for example, at least 92%, for example, at least 95%, for example, 100% of the constituent units according to chemical formula VIII.

[0201] The hydroxyl functional addition polymer may contain constituent units according to Formula VIII in an amount of at least 70%, e.g., at least 80%, e.g., at least 85%, e.g., at least 90%, where % is based on the total constituent units of the hydroxyl functional addition polymer. The hydroxyl functional addition polymer may contain constituent units according to Formula VIII in an amount of 100% or less, e.g., 95% or less, e.g., 92% or less, e.g., 90% or less, where % is based on the total constituent units of the hydroxyl functional addition polymer. The hydroxyl functional addition polymer may contain constituent units according to Formula VIII in an amount of 70% to 95%, e.g., 80% to 95%, e.g., 85% to 95%, e.g., 90% to 95%, e.g., 92% to 95%, e.g., 70% to 92%, e.g., 80% to 92%, e.g., 85% to 92%, e.g., 90% to 92%, e.g., 70% to 90%, e.g., 80% to 90%, e.g., 8580% to 90%, e.g., 85% to 90%, e.g., 80% to 90%, e.g., 85% to 90%, e.g., 70% to 90%, e.g., 80% to 90%, e.g., 85% to 90%, e.g., 80% to 90%, e.g., 85% to 90%, e.g., 80% to 90%, e.g., 80% to 90%, e.g., 80% to 90%, e.g., 80% to 90%, e.g., 80% to 90%, e.g., 80% to 90%, e.g., 80% to 90%

[0202] The hydroxyl-functional addition polymer may optionally further comprise a constituent unit containing residues of a vinyl ester. The vinyl ester may comprise any suitable vinyl ester. For example, the vinyl ester is of the formula C(R 1 )2==C(R 1 It can follow )(C(O)CH3), and each R 1It is independently one of hydrogen, an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an alkylcycloalkyl group, a substituted alkylcycloalkyl group, a cycloalkylalkyl group, a substituted cycloalkylalkyl group, an aryl group, a substituted aryl group, an alkylaryl group, a substituted alkylaryl group, a cycloalkylaryl group, a substituted cycloalkylaryl group, an arylalkyl group, a substituted arylalkyl group, an arylcycloalkyl group, or a substituted arylcycloalkyl group. Non-limiting examples of suitable vinyl esters include vinyl acetate, vinyl formate, or any combination thereof.

[0203] A hydroxyl-functional addition polymer can be formed by polymerizing vinyl ester monomers to form an intermediate polymer comprising constituent units containing vinyl ester residues, and then hydrolyzing the constituent units containing vinyl ester residues of the intermediate polymer to form a hydroxyl-functional addition polymer. The vinyl ester residues may comprise at least 70%, e.g., at least 80%, e.g., at least 85%, e.g., at least 90% of the constituent units comprising the intermediate polymer, where % is based on the total constituent units of the intermediate polymer. The vinyl ester residues may comprise 100% or less, e.g., 95% or less, e.g., 92% or less, e.g., 90% or less of the constituent units comprising the intermediate polymer, where % is based on the total constituent units of the intermediate polymer. The residue of the vinyl ester may comprise 70% to 95%, e.g., 80% to 95%, e.g., 85% to 95%, e.g., 90% to 95%, e.g., 92% to 95%, e.g., 70% to 92%, e.g., 80% to 92%, e.g., 85% to 92%, e.g., 90% to 92%, e.g., 70% to 90%, e.g., 80% to 90%, e.g., 85% to 90% of a hydroxyl-functional addition polymer, and % is based on the total constituent unit of the intermediate polymer.

[0204] The hydroxyl functional addition polymer may have a theoretical hydroxyl equivalent of at least 30 g / hydroxyl group ("OH"), e.g., at least 35 g / OH, e.g., at least 40 g / OH, e.g., at least 44 g / OH. The hydroxyl functional addition polymer may have a theoretical hydroxyl equivalent of 200 g / OH or less, e.g., 100 g / OH or less, e.g., 60 g / OH or less, e.g., 50 g / OH or less. The hydroxyl functional addition polymer is 30 g / OH to 200 g / OH, e.g., 30 g / OH to 100 g / OH, e.g., 30 g / OH to 60 g / OH, e.g., 30 g / OH to 50 g / OH, e.g., 35 g / OH to 200 g / OH, e.g., 35 g / OH to 100 g / OH, e.g., 35 g / OH to 60 g / OH, e.g., 35 g / OH to 50 g / OH, e.g., 40 g / OH to 200 g / OH, e.g., 40 g / OH to 100 g / OH, e.g., 40 g / OH to 60 g / OH, e.g., 40 g / OH to 50 g / OH, e.g., 44 g / OH to 200 g / OH, e.g., 44 g / OH to 100 g / OH, e.g., 44 It may have a theoretical hydroxyl equivalent of g / OH to 60 g / OH, e.g., 44 g / OH to 50 g / OH. As used herein, the term "theoretical hydroxyl equivalent" refers to the weight (grams) of the hydroxyl functional addition polymer resin solid divided by the theoretical equivalent of the hydroxyl groups present in the hydroxyl functional addition polymer, which can be calculated according to the formula (a):

[0205] (a)

[0206] The hydroxyl-functional addition polymer may have a theoretical hydroxyl value of at least 1,000 mg KOH / gram addition polymer, e.g., at least 1,100 mg KOH / gram addition polymer, e.g., at least 1,150 mg KOH / gram addition polymer, e.g., at least 1,200 mg KOH / gram addition polymer. The hydroxyl-functional addition polymer may have a theoretical hydroxyl value of 1,300 mg KOH / gram or less addition polymer, e.g., 1,200 mg KOH / gram or less addition polymer, e.g., 1,150 mg KOH / gram or less addition polymer. The hydroxyl functional addition polymer may have a theoretical hydroxyl value of 1,000 to 1,300 mg KOH / gram addition polymer, e.g., 1,000 to 1,200 mg KOH / gram addition polymer, e.g., 1,000 to 1,150 mg KOH / gram addition polymer, e.g., 1,100 to 1,300 mg KOH / gram addition polymer, e.g., 1,100 to 1,200 mg KOH / gram addition polymer, e.g., 1,100 to 1,150 mg KOH / gram addition polymer, e.g., 1,150 to 1,300 mg KOH / gram addition polymer, e.g., 1,150 to 1,200 mg KOH / gram addition polymer. The term "theoretical hydroxyl value" as used herein refers to the number of milligrams of potassium hydroxide required to neutralize the acetic acid taken upon the acetylation of 1 gram of a chemical containing free hydroxyl groups, and was determined by the theoretical calculation of the number of free hydroxyl groups theoretically present in 1 gram of a hydroxyl-functional addition polymer.

[0207] The hydroxyl functional addition polymer has a number average molecular weight (M) of at least 5,000 g / mol, e.g., at least 20,000 g / mol, e.g., at least 25,000 g / mol, e.g., at least 50,000 g / mol, e.g., at least 75,000 g / mol, e.g., 100,000 g / mol, e.g., 125,000 g / mol, as determined by gel permeation chromatography using polystyrene calibration standards. n ) may have. The hydroxyl functional addition polymer has a number average molecular weight (M) of 500,000 g / mol or less, e.g., 300,000 g / mol or less, e.g., 200,000 or less, e.g., 125,000 g / mol or less, e.g., 100,000 g / mol or less, as determined by gel permeation chromatography using polystyrene calibration standards. nCan have ). The hydroxyl functional addition polymer is 5,000 g / mol to 500,000 g / mol, e.g., 5,000 g / mol to 300,000 g / mol, e.g., 5,000 g / mol to 200,000 g / mol, e.g., 5,000 g / mol to 125,000 g / mol, e.g., 5,000 g / mol to 100,000 g / mol, e.g., 20,000 g / mol to 500,000 g / mol, e.g., 20,000 g / mol to 300,000 g / mol, e.g., 20,000 g / mol to 200,000 g / mol, e.g., 20,000 g / mol to 125,000 g / mol, as determined by gel permeation chromatography using polystyrene calibration standards. g / mol, e.g., 20,000 g / mol to 100,000 g / mol, e.g., 25,000 g / mol to 500,000 g / mol, e.g., 25,000 g / mol to 300,000 g / mol, e.g., 25,000 to 200,000 g / mol, e.g., 25,000 g / mol to 125,000 g / mol, e.g., 25,000 g / mol to 100,000 g / mol, e.g., 50,000 g / mol to 500,000 g / mol, e.g., 50,000 g / mol to 300,000 g / mol, e.g., 50,000 g / mol to 200,000 g / mol, e.g., 50,000 g / mol to 125,000 g / mol, e.g., 50,000 g / mol to 100,000 g / mol, e.g., 75,000 g / mol to 500,000 g / mol, e.g., 75,000 g / mol to 300,000 g / mol, e.g., 75,000 g / mol to 200,000 g / mol, e.g., 75,000 g / mol to 125,000 g / mol, e.g., 100,000 g / mol to 500,000 g / mol, e.g., 100,000 g / mol to 300,000 g / mol,For example, a number average molecular weight (M) of 100,000 g / mol to 200,000 g / mol, for example, 100,000 g / mol to 125,000 g / mol n Can have ).

[0208] The hydroxyl functional addition polymer has a weight-average molecular weight (M) of at least 5,000 g / mol, e.g., at least 20,000 g / mol, e.g., at least 25,000 g / mol, e.g., at least 50,000 g / mol, e.g., at least 75,000 g / mol, e.g., 100,000 g / mol, e.g., 125,000 g / mol, e.g., at least 150,000 g / mol, e.g., at least 200,000 g / mol, e.g., at least 250,000 g / mol, e.g., at least 300,000 g / mol, as determined by gel permeation chromatography using polystyrene calibration standards. w ) may have. The hydroxyl functional addition polymer has a weight-average molecular weight (M) of 500,000 g / mol or less, e.g., 300,000 g / mol or less, e.g., 200,000 or less, e.g., 125,000 g / mol or less, e.g., 100,000 g / mol or less, as determined by gel permeation chromatography using polystyrene calibration standards. wCan have ). The hydroxyl functional addition polymer is 5,000 g / mol to 500,000 g / mol, e.g., 5,000 g / mol to 300,000 g / mol, e.g., 5,000 g / mol to 200,000 g / mol, e.g., 5,000 g / mol to 125,000 g / mol, e.g., 5,000 g / mol to 100,000 g / mol, e.g., 20,000 g / mol to 500,000 g / mol, e.g., 20,000 g / mol to 300,000 g / mol, e.g., 20,000 g / mol to 200,000 g / mol, e.g., 20,000 g / mol to 125,000 g / mol, as determined by gel permeation chromatography using polystyrene calibration standards. g / mol, e.g., 20,000 g / mol to 100,000 g / mol, e.g., 25,000 g / mol to 500,000 g / mol, e.g., 25,000 g / mol to 300,000 g / mol, e.g., 25,000 to 200,000 g / mol, e.g., 25,000 g / mol to 125,000 g / mol, e.g., 25,000 g / mol to 100,000 g / mol, e.g., 50,000 g / mol to 500,000 g / mol, e.g., 50,000 g / mol to 300,000 g / mol, e.g., 50,000 g / mol to 200,000 g / mol, e.g., 50,000 g / mol to 125,000 g / mol, e.g., 50,000 g / mol to 100,000 g / mol, e.g., 75,000 g / mol to 500,000 g / mol, e.g., 75,000 g / mol to 300,000 g / mol, e.g., 75,000 g / mol to 200,000 g / mol, e.g., 75,000 g / mol to 125,000 g / mol, e.g., 100,000 g / mol to 500,000 g / mol, e.g., 100,000 g / mol to 300,000 g / mol,For example, 100,000 g / mol to 200,000 g / mol, for example, 100,000 g / mol to 125,000 g / mol, for example, 125,000 g / mol to 500,000 g / mol, for example, 125,000 g / mol to 300,000 g / mol, for example, 125,000 g / mol to 200,000 g / mol, for example, 150,000 g / mol to 500,000 g / mol, for example, 150,000 g / mol to 300,000 g / mol, for example, 150,000 g / mol to 200,000 g / mol, for example, 200,000 g / mol to 500,000 g / mol, for example, 200,000 It may have a weight average molecular weight of g / mol to 300,000 g / mol, e.g., 250,000 g / mol to 500,000 g / mol, e.g., 250,000 g / mol to 300,000 g / mol, e.g., 300,000 g / mol to 500,000 g / mol.

[0209] Unless otherwise stated, the term "number average molecular weight (M)" as used herein n )" and "weight-average molecular weight (M w )" is the number average molecular weight (M) as determined by gel permeation chromatography using a Waters 2695 separation module equipped with a Waters 410 differential refractometer (RI detector), polystyrene standards having a molecular weight of approximately 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 a single Asahipak GF-510 HQ column for separation. z ) and weight-average molecular weight (M w It means ).

[0210] The hydroxyl functional addition polymer has a z-average molecular weight (M) of at least 10,000 g / mol, e.g., at least 15,000 g / mol, e.g., at least 20,000 g / mol, as determined by gel permeation chromatography using a polystyrene calibration standard. z ) may have. The hydroxyl functional addition polymer has a z-average molecular weight (M) of 35,000 g / mol or less, e.g., 25,000 g / mol or less, e.g., 20,000 g / mol or less, as determined by gel permeation chromatography using polystyrene calibration standards. z ) may have. The hydroxyl functional addition polymer has a z-average molecular weight (M) of 10,000 g / mol to 35,000 g / mol, e.g., 10,000 g / mol to 25,000 g / mol, e.g., 10,000 g / mol to 20,000 g / mol, e.g., 15,000 g / mol to 35,000 g / mol, e.g., 15,000 g / mol to 25,000 g / mol, e.g., 15,000 g / mol to 20,000 g / mol, e.g., 20,000 g / mol to 35,000 g / mol, e.g., 20,000 g / mol to 25,000 g / mol, e.g., 20,000 g / mol to 25,000 g / mol, as determined by gel permeation chromatography using polystyrene calibration standards. z Can have ).

[0211] According to the present disclosure, a 4 wt% solution of a water-soluble hydroxyl-functional addition polymer may have a viscosity of at least 10 cP, e.g., at least 15 cP, e.g., at least 20 cP at 20°C when measured using a Brookfield synchronous motor rotary type viscometer. A 4 wt% solution of a water-soluble hydroxyl-functional addition polymer may have a viscosity of 110 cP or less, e.g., 90 cP or less, e.g., 70 cP or less, e.g., 60 cP or less, e.g., 50 cP or less, e.g., 40 cP or less at 20°C when measured using a Brookfield synchronous motor rotary type viscometer. A 4 wt% solution of a water-soluble hydroxyl-functional addition polymer may have a viscosity of 10 to 110 cP, e.g., 10 to 90 cP, e.g., 10 to 70 cP, e.g., 10 to 50 cP, e.g., 10 to 40 cP, e.g., 15 to 110 cP, e.g., 15 to 90 cP, e.g., 15 to 70 cP, e.g., 15 to 60 cP, e.g., 15 to 50 cP, e.g., 15 to 40 cP, e.g., 20 to 110 cP, e.g., 20 to 90 cP, e.g., 20 to 70 cP, e.g., 20 to 60 cP, e.g., 20 to 50 cP, e.g., 20 to 40 cP, e.g., 20 to 40 cP, when measured using a Brookfield synchronous motor rotary type viscometer. there is.

[0212] According to the present disclosure, the hydroxyl-functional addition polymer described above may be present in the electrodeposited coating composition in an amount of at least 0.01 wt%, e.g., at least 0.1 wt%, e.g., at least 0.3 wt%, e.g., at least 0.5 wt%, e.g., at least 0.75 wt%, e.g., 1 wt%, based on the total weight of the resin solid of the electrodeposited coating composition. The hydroxyl-functional addition polymer described above may be present in the electrodeposited coating composition in an amount of 5 wt% or less, e.g., 3 wt% or less, e.g., 2 wt% or less, e.g., 1.5 wt% or less, e.g., 1 wt% or less, e.g., 0.75 wt% or less, based on the total weight of the resin solid of the electrodeposited coating composition. The hydroxyl functional addition polymer is present in an amount of 0.01 wt% to 5 wt%, e.g., 0.01 wt% to 3 wt%, e.g., 0.01 wt% to 2 wt%, e.g., 0.01 wt% to 1.5 wt%, e.g., 0.01 wt% to 1 wt%, e.g., 0.01 wt% to 0.75 wt%, e.g., 0.1 wt% to 5 wt%, e.g., 0.1 wt% to 3 wt%, e.g., 0.1 wt% to 2 wt%, e.g., 0.1 wt% to 1.5 wt%, e.g., 0.1 wt% to 1 wt%, e.g., 0.1 wt% to 0.75 wt%, e.g., 0.3 wt% to 5 wt%, e.g., 0.3 wt% to 3 wt%, e.g., 0.3 wt% to 2 wt%, based on the total weight of the resin solid of the electrodepositable coating composition. For example, 0.3 wt% to 1.5 wt%, for example, 0.3 wt% to 1 wt%, for example, 0.3 wt% to 0.75 wt%, for example, 0.5 wt% to 5 wt%, for example, 0.5 wt% to 3 wt%, for example, 0.5 wt% to 2 wt%, for example, 0.5 wt% to 1.5 wt%, for example, 0.5 wt% to 1 wt%, for example, 0.5 wt% to 0.It may be present in the electrodepositable coating composition in an amount of 75 weight%, for example, 1 weight% to 5 weight%, for example, 1 weight% to 3 weight%, for example, 1 weight% to 2 weight%, for example, 1 weight% to 1.5 weight%.

[0213] Cellulose As described above, the edge control adduct may include a water-soluble cellulose derivative. The water-soluble cellulose derivative may include hydroxyethyl cellulose, carboxymethyl cellulose, carboxymethylhydroxyethyl cellulose, hydroxymethyl cellulose, carboxyethyl cellulose, salts thereof, and combinations thereof. For example, the water-soluble cellulose derivative may include carboxymethylcellulose and a salt thereof (CMC). CMC is a cellulose ether in which a portion of the hydroxyl group on the anhydroglucose ring is substituted with a carboxymethyl group. The degree of carboxymethyl substitution may range from 0.4 to 3. Since CMC is a long-chain polymer, its viscosity in aqueous solution depends on its molecular weight, which may vary between 50,000 and 2,000,000 g / mol on a weight average basis. Carboxymethylcellulose may have a weight-average molecular weight of at least 50,000, e.g., at least 100,000, or in some cases, at least 200,000, e.g., 50,000 to 1,000,000, 100,000 to 500,000, or 200,000 to 300,000 g / mol. The degree of substitution and the viscosity of the aqueous solution can be determined via ASTM D 1439-03. The molecular weight is typically estimated from the viscosity of a standard CMC solution.

[0214] A water-soluble cellulose derivative may be present in the electrodepositable coating composition in an amount of at least 0.001% by weight, for example, at least 0.05% by weight, for example, 0.001% to 10% or 0.05% to 2% based on the total weight of the resin solid.

[0215] Polyvinyl formamide polymerAs described above, the edge control adduct may comprise a polyvinyl formamide polymer. The polyvinyl formamide polymer may not be hydrolyzed or may be partially or completely hydrolyzed. Hydrolysis of the formamide group provides a primary amine group, and complete hydrolysis of the polyvinyl formamide polymer provides a poly(vinyl amine). Hydrolyzed polyvinyl formamide polymers are commercially available from BASF under the trademark "LUAMIN®" with various weight-average molecular weights (about 340,000 daltons to less than 10,000 daltons) and various degrees of hydrolysis (10%, 30%, and 90%). Additionally, the unhydrolyzed or hydrolyzed polyvinyl formamide polymers may comprise monomer units other than vinylamide and vinyl amine monomer units. For example, vinyl formamide can be copolymerized with vinyl acetate, and the hydrolysis of the resulting copolymer can provide vinyl alcohol monomer units as well as vinyl amine monomer units. In another example, the polyvinyl formamide polymer comprises only vinyl amide and vinyl amine monomer units (i.e., the polyvinyl formamide polymer is a homopolymer of vinyl formamide or at least a partially hydrolyzed homopolymer of vinyl formamide).

[0216] The electrodepositable coating composition generally contains a non-hydrolyzed or hydrolyzed polyvinyl formamide polymer in an amount of less than 1 weight percent of the coating composition. For example, the electrodepositable coating composition may contain at least about 25 ppm by weight of the non-hydrolyzed or hydrolyzed polyvinyl formamide polymer, and in another example, the aqueous electrodepositable coating composition may contain at least about 50 ppm by weight of the non-hydrolyzed or hydrolyzed polyvinyl formamide polymer. For example, the aqueous electrodepositable coating composition may contain up to about 1000 ppm by weight of the non-hydrolyzed or hydrolyzed polyvinyl formamide polymer, and in another example, the electrodepositable coating composition may contain up to about 100 ppm by weight of the non-hydrolyzed or hydrolyzed polyvinyl formamide polymer. The optimal amount of non-hydrolyzed or hydrolyzed polyvinyl formamide polymer for a specific aqueous electrodeposition coating composition can be simply determined, and generally satisfactory results can be achieved with an amount of non-hydrolyzed or hydrolyzed polyvinyl formamide polymer of less than 1000 ppm based on the weight of the aqueous electrodeposition coating composition.

[0217] Cationic epoxy microgelAccording to the present disclosure, the edge control adduct may comprise a cationic epoxy microgel. The cationic epoxy microgel refers to a cationic microgel dispersion that can be prepared by first dispersing a reactive mixture of a cationic polyepoxide-amine reaction product and a polyepoxide crosslinking agent in an aqueous medium. The dispersion step can preferably be achieved by adding the polyepoxide-amine reaction product to a mixture of water and acid at an elevated temperature of 100°C to 150°C to form a cationic dispersion of the resin in water. Typically, the solid content of the resulting dispersion will be about 20% by weight to 50% by weight, and the degree of neutralization will be 20% to 100% of the total theoretical neutralization. The acid may be an organic acid, e.g., formic acid, lactic acid, and acetic acid, as well as an inorganic acid, e.g., phosphoric acid and sulfamic acid. Additionally, a mixture of acids comprising a mixture of organic and inorganic acids may be used. The degree of neutralization depends on the specific reaction product, and generally only an amount of acid sufficient to stabilize the resulting microgel dispersion is added. The expression "cationic polyepoxide-amine reaction product containing primary and / or secondary amine groups" includes primary and secondary amine groups and their acidic salts.

[0218] Polyamine-dialdehyde adductAccording to the present disclosure, a crater control adduct may comprise a polyamine-dialdehyde adduct comprising, or in some cases, a polymerization product of polyamine and dialdehyde, or, in some cases, a polyamine-dialdehyde adduct comprising, or in some cases, essentially composed of, a polyamine and a dialdehyde. Polyamine and a dialdehyde may be polymerized to form a polymerization product. As used herein, "polyamine" comprises a compound comprising at least two amino groups, and the amino groups may comprise primary or secondary amino groups. As used herein, "primary amino group" is a derivative of ammonia in which one hydrogen atom is replaced by an alkyl or aryl group, and "secondary amino group" is a derivative of ammonia in which two hydrogen atoms are replaced by an alkyl or aryl group. Non-limiting examples of polyamine-dialdehyde adducts are described in paragraphs

[0009] through

[0028] of International Publication No. WO 2018 / 005869 A1, the referenced portions thereof are incorporated herein by reference.

[0219] Additional components of an electrodepositable coating composition

[0220] The electrodepositable coating composition according to the present disclosure may optionally include one or more additional components in addition to the active hydrogen-containing ionic base-containing film-forming polymer, at least partially blocked polyisocyanate curing agent, curing catalyst, and edge control adduct described above.

[0221] According to the present disclosure, the electrodepositable coating composition of the present disclosure may optionally include a corrosion inhibitor. Any suitable corrosion inhibitor may be used. For example, the corrosion inhibitor may include a corrosion inhibitor comprising yttrium, lanthanum, cerium, calcium, azole, or any combination thereof.

[0222] Suitable non-limiting examples of azoles include benzotriazole, 5-methylbenzotriazole, 2-aminothiazole, and salts thereof.

[0223] If present, the corrosion inhibitor(s) may be present in the electrodeposited coating composition in an amount of at least 0.001 weight%, e.g., at least 5 weight%, based on the total weight of the electrodeposited coating composition. If present, the corrosion inhibitor(s) may be present in the electrodeposited coating composition in an amount of 25 weight% or less, e.g., 15 weight% or less, e.g., 10 weight% or less, based on the total weight of the electrodeposited coating composition. If present, the corrosion inhibitor(s) may be present in the electrodeposited coating composition in an amount of 0.001 weight% to 25 weight%, e.g., 0.001 weight% to 15 weight%, e.g., 0.001 weight% to 10 weight%, e.g., 5 weight% to 25 weight%, e.g., 5 weight% to 15 weight%, e.g., 5 weight% to 10 weight%, based on the total weight of the electrodeposited coating composition.

[0224] Alternatively, the electrodeposited coating composition may be substantially, essentially, or completely free of corrosion inhibitors.

[0225] According to the present disclosure, the electrodepositable coating composition may optionally further comprise a silane. The silane may comprise functional groups such as, for example, hydroxyl, carbamate, epoxy, isocyanate, amine, amine salt, mercaptan, or combinations thereof. The silane may comprise, for example, aminosilane, mercaptosilane, or combinations thereof. Additionally, a mixture of silanes having unsaturated groups, such as aminosilane and vinyltriacetoxysilane, may be used.

[0226] If present, silane may be present in the electrodepositable coating composition in an amount of at least 0.01 weight%, e.g., at least 0.1 weight%, e.g., at least 1 weight%, e.g., at least 3 weight% based on the total weight of the resin solid. If present, silane may be present in the electrodepositable coating composition in an amount of 5 weight% or less, e.g., 3 weight% or less, e.g., 1 weight% or less based on the total weight of the resin solid. Silane may be present in the electrodepositable coating composition in an amount of 0.01 wt% to 5 wt%, for example, 0.01 wt% to 3 wt%, for example, 0.01 wt% to 1 wt%, for example, 0.1 wt% to 5 wt%, for example, 0.01 wt% to 3 wt%, for example, 0.1 wt% to 1 wt%, for example, 1 wt% to 5 wt%, for example, 1 wt% to 3 wt%, for example, 3 wt% to 5 wt% based on the total weight of the resin solid, if present.

[0227] Alternatively, the electrodepositable coating composition may be substantially, essentially, or completely free of silanes.

[0228] The electrodepositable coating composition may optionally further include a pigment. The pigment may include iron oxide, lead oxide, strontium chromate, carbon black, coal dust, titanium dioxide, barium sulfate, colored pigments, phylosilicate pigments, metal pigments, thermally conductive, electrically insulating fillers, flame-retardant pigments, or any combination thereof.

[0229] The pigment-to-binder (P:B) ratio as presented in the present disclosure may refer to the weight ratio of pigment to binder in the electrodepositable coating composition and / or the weight ratio of pigment to binder in the deposited wet film, and / or the weight ratio of pigment to binder in the dried uncured deposited film, and / or the weight ratio of pigment to binder in the cured film. The pigment-to-binder (P:B) ratio of pigment to electrodepositable binder may be at least 0.05:1, e.g., at least 0.1:1, e.g., at least 0.2:1, e.g., at least 0.30:1, e.g., at least 0.35:1, e.g., at least 0.40:1, e.g., at least 0.50:1, e.g., at least 0.60:1, e.g., at least 0.75:1, e.g., at least 1:1, e.g., at least 1.25:1, e.g., at least 1.5:1. The pigment to binder (P:B) ratio of the pigment to the electrodepositing binder may be 2.0:1 or less, e.g., 1.75:1 or less, e.g., 1.5:1 or less, e.g., 1.25:1 or less, e.g., 1:1 or less, e.g., 0.75:1 or less, e.g., 0.70:1 or less, e.g., 0.60:1 or less, e.g., 0.55:1 or less, e.g., 0.50:1 or less, e.g., 0.30:1 or less, e.g., 0.20:1 or less, e.g., 0.10:1 or less. The pigment to binder (P:B) ratio of the pigment to the electrodepositing binder is 0.05:1 to 2.0:1, e.g., 0.05:1 to 1.75:1, e.g., 0.05:1 to 1.50:1, e.g., 0.05:1 to 1.25:1, e.g., 0.05:1 to 1:1, e.g., 0.05:1 to 0.75:1, e.g., 0.05:1 to 0.70:1, e.g., 0.05:1 to 0.60:1, e.g., 0.05:1 to 0.55:1, e.g., 0.05:1 to 0.50:1, e.g., 0.05:1 to 0.30:1, e.g., 0.05:1 to 0.20:1, e.g., 0.05:1 to 0.10:1, e.g., 0.1:1 to 2.0:1, e.g., 0.1:1 to 1.75:1, e.g., 0.1:1 to 1.50:1, e.g., 0.1:1 to 1.25:1, e.g., 0.1:1 to 1:1, e.g., 0.1:1 to 0.75:1, e.g., 0.1:1 to 0.70:1, e.g., 0.1:1 to 0.60:1, e.g., 0.1:1 to 0.55:1, e.g., 0.1:1 to 0.50:1, e.g., 0.1:1 to 0.30:1, e.g., 0.1:1 to 0.20:1, e.g., 0.2:1 to 2.0:1, e.g., 0.2:1 to 1.75:1, e.g., 0.2:1 to 1.50:1, e.g., 0.2:1 to 1.25:1, e.g., 0.2:1 to 1:1, e.g., 0.2:1 to 0.75:1, e.g., 0.2:1 to 0.70:1, e.g., 0.2:1 to 0.60:1, e.g., 0.2:1 to 0.55:1, e.g., 0.2:1 to 0.50:1, e.g., 0.2:1 to 0.30:1, e.g., 0.3:1 to 2.0:1, e.g., 0.3:1 to 1.75:1, e.g., 0.3:1 to 1.50:1, e.g., 0.3:1 to 1.25:1, e.g., 0.3:1 to 1:1, e.g., 0.3:1 to 0.75:1, e.g., 0.3:1 to 0.70:1, e.g., 0.3:1 to 0.60:1, For example, 0.3:1 to 0.55:1, for example, 0.3:1 to 0.50:1, for example, 0.3:1 to 0.30:1, for example, 0.35:1 to 2.0:1, for example, 0.35:1 to 1.75:1, for example, 0.35:1 to 1.50:1, for example, 0.35:1 to 1.25:1, for example, 0.35:1 to 1:1, for example, 0.35:1 to 0.75:1, for example, 0.35:1 to 0.70:1, for example, 0.35:1 to 0.60:1, for example, 0.35:1 to 0.55:1, for example, 0.35:1 to 0.50:1, for example, 0.4:1 to 2.0:1, for example, 0.4:1 to 1.75:1, e.g., 0.4:1 to 1.50:1, e.g., 0.4:1 to 1.25:1, e.g., 0.4:1 to 1:1, e.g., 0.4:1 to 0.75:1, e.g., 0.4:1 to 0.70:1, e.g., 0.4:1 to 0.60:1, e.g., 0.4:1 to 0.55:1, e.g., 0.4:1 to 0.50:1, e.g., 0.5:1 to 2.0:1, e.g., 0.5:1 to 1.75:1, e.g., 0.5:1 to 1.50:1, e.g., 0.5:1 to 1.25:1, e.g., 0.5:1 to 1:1, e.g., 0.5:1 to 0.75:1, e.g., 0.5:1 to 0.70:1, e.g., 0.5:1 to 0.60:1, e.g., 0.5:1 to 0.55:1, e.g., 0.6:1 to 2.0:1, e.g., 0.6:1 to 1.75:1, e.g., 0.6:1 to 1.50:1, e.g., 0.6:1 to 1.25:1, e.g., 0.6:1 to 1:1, e.g., 0.6:1 to 0.75:1, e.g., 0.6:1 to 0.70:1, e.g., 0.75:1 to 2.0:1, e.g., 0.75:1 to 1.75:1, e.g., 0.75:1 to 1.50:1, e.g., 0.75:1 to 1.25:1, e.g., 0.75:1 to 1:1, e.g., 1:1 to 2.0:1, e.g., 1:1 to 1.75:1, For example, it may be 1:1 to 1.50:1, for example, 1:1 to 1.25:1, for example, 1.25:1 to 2.0:1, for example, 1.25:1 to 1.75:1, for example, 1.25:1 to 1.50:1, for example, 1.50:1 to 2.0:1, for example, 1.50:1 to 1.75:1.

[0230] The electrodepositable coating composition may optionally further comprise a grinding resin. As used herein, the term "grinding resin" refers to a resin that is chemically distinct from the main film-forming polymer, used during the milling of pigments to form a pigment paste, separate from the main film-forming polymer of the binder. For example, the grinding resin may comprise quaternary ammonium bases and / or tertiary sulfonium groups. The grinding resin may be used interchangeably with a grind vehicle.

[0231] Alternatively, the electrodeposited coating composition may optionally be substantially, essentially, or completely free of ground resin. The electrodeposited coating composition used herein is substantially free of ground resin if, if ground resin is present, it is present in an amount of 5 weight percent or less based on the total solid weight of the resin of the composition. The electrodeposited coating composition used herein is essentially free of ground resin if, if ground resin is present, it is present in an amount of 3 weight percent or less based on the total solid weight of the resin of the composition. The electrodeposited coating composition used herein is completely free of ground resin if ground resin is not present in the composition, that is, if it is 0.00 weight percent based on the total solid weight of the resin of the composition.

[0232] The electrodeposited coating composition may be substantially, essentially, or completely free of electrically conductive particles. The electrically conductive particles may comprise any particles capable of conducting electricity. The electrically conductive particles used herein are of a material having at least 1 x 10⁻⁶ at 20°C. 5 Conductivity of S / m and 1 x 10 6If having a resistivity of Wm or less, it is "capable of conducting electricity." The electrically conductive particles may include carbonaceous materials, e.g., activated carbon, carbon black, e.g., acetylene black and furnace black, graphene, carbon nanotubes including single-walled carbon nanotubes and / or multi-walled carbon nanotubes, carbon fibers, fullerenes, metal particles, and combinations thereof. The electrodeposited coating composition used herein is substantially free of electrically conductive particles when the electrically conductive particles are present in an amount of less than 5 weight percent based on the total weight of the pigment in the composition. The electrodeposited coating composition used herein is essentially free of electrically conductive particles when the electrically conductive particles are present in an amount of less than 1 weight percent based on the total weight of the pigment in the composition. The electrodeposited coating composition used herein is completely free of electrically conductive particles when the electrically conductive particles are not present in the composition, i.e., when it is 0.00 weight percent based on the total weight of the pigment in the composition.

[0233] The electrodeposited coating composition may be substantially, essentially, or completely free of metal particles. As used herein, the term "metal particles" refers to metal and metal alloy pigments composed mainly of metal(s) in an elemental (zero-valence) state. Metal particles may include zinc, aluminum, cadmium, magnesium, beryllium, copper, silver, gold, iron, titanium, nickel, manganese, chromium, scandium, yttrium, zirconium, platinum, tin, and alloys thereof, as well as various grades of steel. The electrodeposited coating composition used herein is substantially free of metal particles when metal particles are present in an amount of less than 5 weight percent based on the total weight of the pigment in the composition. The electrodeposited coating composition used herein is essentially free of metal particles when metal particles are present in an amount of less than 1 weight percent based on the total weight of the pigment in the composition. The electrodeposited coating composition used herein is completely free of metal particles when metal particles are not present in the composition, i.e., when 0.00 weight percent based on the total weight of the pigment in the composition.

[0234] The electrodepositable coating compositions of the present disclosure may be substantially, essentially, or completely free of lithium-containing compounds. As used herein, lithium-containing compounds refer to compounds or complexes containing lithium, such as, for example, LiCoC, LiNiC, LiFePO4, LiCoPCO4, LiMnO2, LiMn2O4, Li(NiMnCo)O2, and Li(NiCoAl)O2. As used herein, the electrodepositable coating composition is "substantially free" of lithium-containing compounds if the lithium-containing compounds are present in the electrodepositable coating composition in an amount of less than 1 weight percent based on the total solid weight of the composition. As used herein, the electrodepositable coating composition is "essentially free" of lithium-containing compounds if the lithium-containing compounds are present in the electrodepositable coating composition in an amount of less than 0.1 weight percent based on the total solid weight of the composition. The electrodepositable coating composition used herein is "completely free" of a lithium-containing compound when the lithium-containing compound is not present in the electrodepositable coating composition, that is, when it is <0.001 weight% based on the total solid weight of the composition.

[0235] According to the present disclosure, the electrodepositable coating composition of the present disclosure may optionally include a polyalkylene oxide polymer that may comprise a crater-controlling adduct that may be incorporated into the coating composition, for example, a copolymer of butylene oxide and propylene oxide. According to the present disclosure, the molar ratio of butylene oxide to propylene oxide may be at least 1:1, e.g., at least 3:1, e.g., at least 5:1, and in some cases, 50:1 or less, e.g., 30:1 or less, e.g., 20:1 or less. According to the present disclosure, the molar ratio of butylene oxide to propylene oxide may be 1:1 to 50:1, e.g., 3:1 to 30:1, e.g., 5:1 to 20:1.

[0236] The polyalkylene oxide polymer may comprise at least two hydroxyl functional groups and may be monofunctional, difunctional, trifunctional, or tetrafunctional. As used herein, "hydroxyl functional group" comprises an -OH group. For clarity, the polyalkylene oxide polymer may comprise additional functional groups in addition to the hydroxyl functional group(s).

[0237] The hydroxyl equivalent of the polyalkylene oxide polymer may be 100 g / mol to 2,000 g / mol, e.g., 200 g / mol to 1,000 g / mol, e.g., 400 g / mol to 800 g / mol. As used herein, with respect to the polyalkylene oxide polymer, the “hydroxyl equivalent” is determined by dividing the molecular weight of the polyalkylene oxide polymer by the number of hydroxyl groups present in the polyalkylene oxide polymer.

[0238] The polyalkylene oxide polymer may have a z-average molecular weight of 200 g / mol to 5,000 g / mol, e.g., 400 g / mol to 3,000 g / mol, e.g., 600 g / mol to 2,000 g / mol.

[0239] The polyalkylene oxide polymer may be present in the electrodepositable coating composition in an amount of 0.1% to 10% by weight, e.g., 0.5% to 4% by weight, e.g., 0.75% to 3% by weight, based on the total weight of the resin blend solids.

[0240] According to the present disclosure, the electrodepositable coating composition may further comprise a polyetheramine adduct comprising (a) a reaction product prepared from a reaction product including (1) a polyol; and (2) an epoxy functional material; and (b) a non-gelled ionic reaction product prepared from a reaction product including polyetheramine.

[0241] Examples of suitable polyols useful for forming a non-gelled ionic reaction product include resorcinol, dihydroxybenzene, aliphatic, alicyclic, or non-aliphatic hydroxyl-containing compounds, such as ethylene glycol, propylene glycol, bisphenol A, dihydroxyl cyclohexane, dimethylol cyclohexane, or combinations thereof. The polyol may be present in the polyetheramine adduct in an amount of about 0% to 20% by weight, for example, 0% to 15% by weight, based on the total weight of the reactants forming the polyether reaction product.

[0242] Examples of suitable epoxy functional materials useful for forming non-gelled ionic reaction products include molecules containing at least one epoxy group, such as diglycidyl ethers or polyglycidyl ethers of polyhydric alcohols, such as polyglycidyl epoxy of bisphenol A. Suitable epoxy functional materials may have an epoxy equivalent in the range of about 90 to about 2000, as measured by titration with perchloric acid using methyl violet as an indicator. The epoxy functional material may comprise about 10% to 40% by weight based on the total weight of the epoxy functional polyester, for example, 15% to 35% by weight of the epoxy functional material combines with or reacts with the polyester described above to form the epoxy functional polyester.

[0243] According to the present disclosure, a polyetheramine adduct may be formed by reacting a non-gelled ionic reaction product with at least one polyetheramine that may be identical to the one described above, for example, one of the Jeffamine series products (commercially available from Huntsman Corporation), which is characterized in that the polyetheramine features repeating units of propylene oxide, ethylene oxide, or a mixture of propylene oxide and ethylene oxide in its respective structure. Examples of such polyetheramines include amination propoxylated pentaerythritol, such as Jeffamine XTJ-616 and those represented by formulas (I) through (III) above.

[0244] Additional examples of polyetheramine adducts are described in U.S. Patents No. 4,420,574 and 4,423,166, which are incorporated herein by reference.

[0245] According to the present disclosure, a polyetheramine adduct may be present in an electrodepositable coating composition in an amount of at least 3% by weight, e.g., at least 5% by weight, e.g., at least 10% by weight, e.g., at least 15% by weight, e.g., 20% by weight or less, e.g., 15% by weight or less, e.g., 10% by weight or less, e.g., 5% by weight or less, e.g., 5% by weight or less, based on the total weight of the resin-compounded solid. The polyetheramine adduct may be present in an amount of 3% to 20% by weight, e.g., 5% to 15% by weight, e.g., 5% to 10% by weight, based on the total weight of the resin-compounded solid.

[0246] According to the present disclosure, the electrodepositable coating composition may include other optional components, e.g., various additives, e.g., fillers, plasticizers, antioxidants, biocides, UV light absorbers and stabilizers, sterically hindered amine light stabilizers, defoamers, fungicides, dispersion aids, flow control agents, surfactants, wetting agents, or combinations thereof, if necessary. Alternatively, the electrodepositable coating composition may be entirely free of any optional components, that is, the optional components are not present in the electrodepositable coating composition. The other additives mentioned above may be present in the electrodepositable coating composition in an amount of 0.01% to 3% by weight based on the total weight of the resin solid of the electrodepositable coating composition.

[0247] The electrodepositable coating composition may optionally further include bis[2-(2-butoxyethoxy)ethoxy]methane. Bis[2-(2-butoxyethoxy)ethoxy]methane may be present in an amount of at least 0.1 wt%, e.g., at least 0.5 wt%, based on the weight of the resin solid. Bis[2-(2-butoxyethoxy)ethoxy]methane may be present in an amount of 15 wt% or less, e.g., 10 wt% or less, e.g., 3 wt% or less, based on the weight of the resin solid. Bis[2-(2-butoxyethoxy)ethoxy]methane may be present in an amount of 0.1% to 15% by weight, e.g., 0.1% to 10% by weight, e.g., 0.1% to 3% by weight, e.g., 0.5% to 15% by weight, e.g., 0.5% to 10% by weight, e.g., 0.5% to 3% by weight, based on the weight of the resin solid.

[0248] According to the present disclosure, the electrodepositable coating composition may comprise water and / or one or more organic solvent(s). Water may be present in an amount of, for example, 40% to 90% by weight, e.g., 50% to 75% by weight, based on the total weight of the electrodepositable coating composition. Examples of suitable organic solvents include oxygenated organic solvents containing 1 to 10 carbon atoms in an alkyl group, e.g., monoalkyl ethers of ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol, e.g., monoethyl ethers and monobutyl ethers of these glycols. Other examples of at least partially water-miscible solvents include alcohols, e.g., ethanol, isopropanol, butanol, and diacetone alcohol. When used, the organic solvent may typically be present in an amount of less than 10% by weight, e.g., less than 5% by weight, based on the total weight of the electrodepositable coating composition. The electrodepositable coating composition may be provided in the form of a dispersion, for example, an aqueous dispersion.

[0249] According to the present disclosure, the total solid content of the electrodepositable coating composition may be at least 1 weight%, for example, at least 5 weight%, based on the total weight of the electrodepositable coating composition, and may be 50 weight% or less, for example, 40 weight% or less, for example, 20 weight% or less. The total solid content of the electrodepositable coating composition may be 1 weight% to 50 weight%, for example, 5 weight% to 40 weight%, for example, 5 weight% to 20 weight% based on the total weight of the electrodepositable coating composition. As used herein, "total solid" refers to the non-volatile contents of the electrodepositable coating composition, that is, a substance that does not volatilize when heated to 110°C for 15 minutes.

[0250] write

[0251] According to the present disclosure, an electrodepositable coating composition may be applied electrophoretically to a substrate. A cationic electrodepositable coating composition may be electrophoretically deposited on any electrically conductive substrate. Suitable substrates include metal substrates, metal alloy substrates, and / or metallized substrates such as nickel-plated plastics. Additionally, the substrate may include a non-metallic conductive material, such as a composite material containing carbon fibers or conductive carbon, for example. According to the present disclosure, the metal or metal alloy may include cold-rolled steel, hot-rolled steel, steel coated with zinc, zinc compounds, or zinc alloy metals, such as electro-galvanized steel, hot-dip galvanized steel, galvanized steel, and steel plated with zinc alloys. Aluminum alloys of the 2XXX, 3XXX, 4XXX, 5XXX, 6XXX, or 7XXX series, as well as A356 series clad aluminum alloys and cast aluminum alloys, may also be used as substrates. Additionally, magnesium alloys of the AZ31B, AZ91C, AM60B, or EV31A series may be used as substrates. Furthermore, the substrates used in this disclosure may include titanium and / or titanium alloys. Other suitable non-ferrous metals include copper and magnesium and alloys of these materials. Metal substrates suitable for use in this disclosure are often vehicle bodies (e.g., Without limitation, includes use in the assembly of doors, body panels, trunk deck lids, roof panels, hoods, roofs and / or stringers, rivets, landing gear components and / or skins used in aircraft, vehicle frames, vehicle parts, motorcycles, wheels, industrial structures and parts, household appliances including washing machines, dryers, refrigerators, stoves, dishwashers, etc., agricultural equipment, lawn and garden equipment, air conditioning units, heat pump units, lawn furniture and other articles. As used herein, "vehicle" or variations thereof include, but are not limited to, civil, commercial and military aircraft and / or land vehicles, such as cars, motorcycles and / or trucks. Additionally, the metal substrate may be in the form of, for example, a metal sheet or a manufactured part. Additionally, it will be understood that the description may be pretreated with a pretreatment solution comprising a zinc phosphate pretreatment solution as described, for example, in U.S. Patents No. 4,793,867 and No. 5,588,989, or a zirconium-containing pretreatment solution as described in U.S. Patents No. 7,749,368 and No. 8,673,091.

[0252] Coating method, coating and coated substrate

[0253] Additionally, the present disclosure relates to a method for coating a substrate such as any one of the electrically conductive substrates mentioned above. According to the present disclosure, such a method may include the steps of electrophoretically applying an electrodepositable coating composition as described above to at least a portion of a substrate and curing the coating composition to form at least partially cured coatings on the substrate. According to the present disclosure, the method may include the steps of (a) electrophoretically depositing the electrodepositable coating composition of the present disclosure onto at least a portion of a substrate and (b) heating the coated substrate to a temperature sufficient for curing the electrodeposited coating on the substrate and for a time sufficient for curing the electrodeposited coating. According to the present disclosure, the method may optionally further include the steps of (c) directly applying one or more pigment-containing coating compositions and / or one or more pigment-free coating compositions to at least a portion of the at least partially cured electrodeposited coating to form a topcoat on at least a portion of the at least partially cured electrodeposited coating, and (d) heating the coated substrate of step (c) to a temperature sufficient for a time sufficient for curing the topcoat.

[0254] According to the present disclosure, the cationic electrodepositable coating composition of the present disclosure may be deposited on 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. After contact with the composition, an adhesive film of the coating composition is deposited on the cathode when a sufficient voltage is applied between the electrodes. The conditions under which electrodeposition is performed are generally similar to those used for electrodeposition of other types of coatings. The applied voltage may vary, for example, from 1 volt to high volts ranging from thousands of volts, e.g., 50 to 500 volts. The current density may be 0.5 to 15 amperes per square foot and tends to decrease during electrodeposition, which indicates the formation of an insulating film.

[0255] Once a cationic electrodepositable coating composition is electrodeposited onto at least a portion of an electrically conductive substrate, the coated substrate is heated at a temperature and for a time sufficient to at least partially cure the electrodeposited coating on the substrate. As used herein with respect to coatings, the term “at least partially cured” refers to a coating formed by applying the coating composition to curing conditions such that a chemical reaction of at least some of the reactive groups of the components of the coating composition occurs to form the coating. The coated substrate may be heated to a temperature in the range of, for example, 250°F to 450°F (121.1°C to 232.2°C), for example, 275°F to 400°F (135°C to 204.4°C), for example, 300°F to 360°F (149°C to 180°C). The curing time may depend not only on the curing temperature but also on other variables, for example, the film thickness of the electrodeposited coating, the level and type of catalyst present in the composition, etc. For the purposes of the present disclosure, all that is needed is a sufficient amount of time to cure the coating on the substrate. For example, the curing time may be in the range of 10 to 60 minutes, e.g., 20 to 40 minutes. The thickness of the resulting cured electrodeposited coating may be in the range of 15 to 50 microns.

[0256] According to the present disclosure, the anionic electrodepositable coating composition of the present disclosure may be deposited on 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. After contact with the composition, an adhesive film of the coating composition is deposited on the anode when a sufficient voltage is applied between the electrodes. The conditions under which electrodeposition is performed are generally similar to those used for electrodeposition of other types of coatings. The applied voltage may vary, for example, from 1 volt to high volts ranging from thousands of volts, e.g., 50 to 500 volts. The current density may be 0.5 to 15 amperes per square foot and tends to decrease during electrodeposition, which indicates the formation of an insulating film.

[0257] Once an anionic electrodepositable coating composition is electrodeposited onto at least a portion of an electrically conductive substrate, the coated substrate is heated at a temperature and for a time sufficient to at least partially cure the electrodeposited coating on the substrate. As used herein with respect to coatings, the term “at least partially cured” refers to a coating formed by applying the coating composition to curing conditions such that a chemical reaction of at least some of the reactive groups of the components of the coating composition occurs to form the coating. The coated substrate may be heated to a temperature in the range of, for example, 200°F to 450°F (93°C to 232.2°C), for example, 275°F to 400°F (135°C to 204.4°C), for example, 300°F to 360°F (149°C to 180°C). The curing time may depend not only on the curing temperature but also on other variables, for example, the film thickness of the electrodeposited coating, the level and type of catalyst present in the composition, etc. For the purposes of this disclosure, all that is needed is a time sufficient to cure the coating on the substrate. For example, the curing time may be in the range of 10 to 60 minutes, e.g., 20 to 40 minutes. The thickness of the resulting cured electrodeposited coating may be in the range of 15 to 50 microns.

[0258] Additionally, the electrodepositable coating composition of the present disclosure may be applied to a substrate using non-electrophoretic coating application techniques, such as flow, immersion, spraying, and roll coating, if necessary. For non-electrophoretic coating application, the coating composition may be applied to non-conductive substrates, such as glass, wood, and plastic, as well as conductive substrates.

[0259] The present disclosure relates to a coating formed by at least partially curing an electrodepositable coating composition further described herein.

[0260] The present disclosure relates to a substrate that is further partially coated with an electrodepositable coating composition described herein in a partially cured state. The coated substrate may comprise a coating comprising (a) an active hydrogen-containing ionic base-containing film-forming polymer; (b) at least partially blocked polyisocyanate curing agent; (c) a curing catalyst; and (d) an edge control adduct, wherein the electrodepositable coating composition has a gel point of less than 150°C as measured by a gel point test method, an edge coverage of greater than 20% as measured by an edge coverage test method, and an Ra of 0.45 or less as measured by a surface roughness test method.

[0261] The electrodepositable coating composition of the present disclosure can be utilized in an electrocoating layer that is part of a multilayer coating composite comprising a substrate having various coating layers. The coating layer is a pretreatment layer, for example, a phosphate layer ( for exampleThe electrocoating layer formed from the aqueous resin dispersion of the present disclosure and a suitable topcoat layer (e.g., a base coat, a clear coat layer, a colored monocoat, and a color-plus-clear composite composition) may be included. The suitable topcoat layer comprises any topcoat layer known in the art, and it is understood that each may independently be in the form of an aqueous, solvent-based, solid particulate (i.e., powder coating composition), or powder slurry. The topcoat typically comprises a film-forming polymer, a crosslinking agent, and, if it is a colored base coat or monocoat, one or more pigments. According to the present disclosure, a primer layer is deposited between the electrocoating layer and the base coat layer. According to the present disclosure, one or more topcoat layers are applied over a substantially uncured base layer. For example, a clear coat layer may be applied over at least a portion of a substantially uncured base coat layer (wet-on-wet), and both layers may be cured simultaneously in a downstream process.

[0262] In addition, the top coat layer can be applied directly onto the electrodeposited coating layer. That is, the substrate lacks a primer layer. For example, the base coat layer can be applied directly onto at least a portion of the electrodeposited coating layer.

[0263] In addition, it will be understood that a top coat layer can be applied to a base layer even if the base layer has not been fully cured. For example, a clear coat layer can be applied to a base coat layer even if the base coat layer has not undergone a curing step. Subsequently, both layers can be cured during a subsequent curing step, so there may be no need to cure the base coat layer and the clear coat layer separately.

[0264] According to the present disclosure, additional components, such as colorants and fillers, may be present in various coating compositions in which a topcoat layer is formed. Any suitable colorant and filler may be used. For example, the colorant may be added to the coating in any suitable form, such as separate particles, dispersions, solutions, and / or flakes. A single colorant or a mixture of two or more colorants may be used in the coating of the present disclosure. Generally, it should be noted that the colorant may be present in any amount sufficient to impart the desired properties, visual and / or color effects in the layers of the multilayer composite.

[0265] Exemplary colorants include pigments, dyes, and tints, such as those used in the paint industry and / or listed by the Dry Color Manufacturers Association (DCMA), as well as those in special effect compositions. Colorants may comprise, for example, finely divided solid powders that are insoluble or wettable under conditions of use. Colorants may be organic or inorganic and may or may not aggregate. Colorants may be incorporated into the coating by grinding or simple mixing. Colorants may be incorporated into the coating by the use of a grinding vehicle, such as an acrylic grinding vehicle, the use of which will be familiar to those skilled in the art.

[0266] Exemplary pigments and / or pigment compositions include, but are not limited to, carbazole dioxazine raw pigment, azo, monoazo, disazo, naphthol AS, salt form (lake), benzimidazolone, condensate, metal complex, isoindolinone, isoindoline and polycyclic phthalocyanine, quinacridone, perylene, perinone, diketopyrrolopyrrole, thioindigo, anthraquinone, indantron, anthrapyrimidine, flavantron, pyrantron, antantron, dioxazine, triarylcarbonium, quinophthalone pigment, diketopyrrolopyrrole red ("DPP Red BO"), titanium dioxide, carbon black, zinc oxide, antimony oxide, etc. and organic or inorganic UV opaque pigments such as iron oxide, transparent red or yellow iron oxide, phthalocyanine blue and mixtures thereof. The terms "pigment" and "colored filler" may be used interchangeably.

[0267] Exemplary dyes include, but are not limited to, acid dyes, azo dyes, basic dyes, direct dyes, disperse dyes, reactive dyes, solvent dyes, sulfur dyes, mordant dyes, and solvent and / or aqueous dyes such as, for example, bismuth vanadate, anthraquinone, perylene, aluminum, quinacridone, thiazole, thiazine, azo, indigoid, nitro, nitroso, oxazine, phthalocyanine, quinoline, stilbene, and triphenylmethane.

[0268] Exemplary tints include, but are not limited to, pigments dispersed in water-based or water-miscible carriers such as AQUA-CHEM 896 commercially available from Degussa, Inc., CHARISMA colorants commercially available from Accurate Dispersions Division of Eastman Chemical, Inc., and MAXITONER INDUSTRIAL colorants.

[0269] The colorant may be in the form of a dispersion, including but not limited to a nanoparticle dispersion. The nanoparticle dispersion may comprise one or more highly dispersed nanoparticle colorants and / or colorant particles to produce a desired visible color and / or opacity and / or visual effect. The nanoparticle dispersion may comprise a colorant such as a pigment or dye having a particle size of less than 150 nm, e.g., less than 70 nm or less than 30 nm. Nanoparticles may be produced by milling stock organic or inorganic pigments using a grinding medium having a particle size of less than 0.5 mm. An exemplary nanoparticle dispersion and a method for preparing the same are identified in U.S. Patent No. 6,875,800 B2, which is incorporated herein by reference. Additionally, nanoparticle dispersions may be produced by crystallization, precipitation, vapor condensation, and chemical abrasion (i.e., partial dissolution). To minimize the re-aggregation of nanoparticles within a coating, a dispersion of resin-coated nanoparticles may be used. As used herein, “dispersion of resin-coated nanoparticles” refers to a continuous phase in which distinct “composite microparticles” comprising nanoparticles and a resin coating on the nanoparticles are dispersed. Exemplary dispersions of resin-coated nanoparticles and methods for preparing the same are identified in U.S. Patent Application No. 10 / 876,031 (filed June 24, 2004, which is incorporated herein by reference) and U.S. Patent Application No. 60 / 482,167 (filed June 24, 2003, which is incorporated herein by reference).

[0270] According to the present disclosure, a special effect composition that may be used in one or more layers of a multilayer coating composite comprises pigments and / or compositions that produce one or more appearance effects such as reflectance, pearlescent luster, metallic luster, phosphorescence, fluorescence, photochromic, photosensitive, thermochromic, stereochromic, and / or color change. Additional special effect compositions may provide other perceptible properties such as reflectivity, opacity, or texture. For example, a special effect composition may produce a color change that causes the color of the coating to change when the coating is viewed from different angles. An exemplary color effect composition is described in U.S. Patent No. 6,894,086. Additional color effect compositions may include transparent coated mica and / or synthetic mica, coated silica, coated alumina, transparent liquid crystal pigments, liquid crystal coatings, and / or any composition in which interference is produced due to a difference in refractive index within the material rather than due to a difference in refractive index between the surface of the material and air.

[0271] According to the present disclosure, a photosensitive composition and / or photochromic composition, which reversibly changes color when exposed to one or more light sources, may be used in multiple layers of a multilayer composite. The photochromic and / or photosensitive composition may be activated by exposure to radiation of a specific wavelength. When the composition is excited, its molecular structure changes, and the altered structure exhibits a new color different from the original color of the composition. When exposure to radiation is removed, the photochromic and / or photosensitive composition may return to a resting state, where the original color of the composition is restored. For example, the photochromic and / or photosensitive composition may be colorless in a non-excited state and may exhibit color in an excited state. The full color change may occur within milliseconds to minutes, e.g., 20 to 60 seconds. An exemplary photochromic and / or photosensitive composition comprises a photochromic dye.

[0272] According to the present disclosure, a photosensitive composition and / or photochromic composition may be associated with and / or at least partially bonded to a polymeric material of a polymer and / or polymerizable component, for example, by covalent bonding. In contrast to some coatings where the photosensitive composition may migrate out of the coating and crystallize into the substrate, the photosensitive composition and / or photochromic composition according to the present disclosure that associates with and / or at least partially bonded to a polymer and / or polymerizable component minimizes migration out of the coating. Exemplary photosensitive compositions and / or photochromic compositions and methods for preparing the same are identified in U.S. Patent Application No. 10 / 892,919 (filed July 16, 2004) and are incorporated herein by reference.

[0273] For the purposes of the detailed description of the invention, it should be understood that the present disclosure may assume alternative variations and sequences of steps, except as otherwise expressly stated. Furthermore, except for any operational examples or otherwise indicated, all numbers expressing the amounts of components used, for example, in the specification and claims, should be understood as being modified in all cases by the term “about.” Accordingly, unless otherwise stated, the numerical parameters presented in the following specification and appended claims are approximations that may vary depending on the desired characteristics to be obtained by the present disclosure. At least, without attempting to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should be interpreted in light of at least the reported significant digits and by applying general rounding techniques.

[0274] Although the numerical ranges and parameters present in the broad scope of this disclosure are approximations, the numerical values ​​presented in specific embodiments are reported as accurately as possible. However, any numerical value inherently includes certain errors inevitably generated by the standard deviation found in each test measurement.

[0275] In addition, it should be understood that any numerical range mentioned herein is intended to include all sub-ranges contained therein. For example, the range “1 to 10” is intended to include all sub-ranges between (and including) the mentioned minimum value 1 and the mentioned maximum value 10. That is, the minimum value is 1 or greater and the maximum value is 10 or less.

[0276] As used herein, “include,” “contain,” and similar terms are understood to be synonymous with “include” in the context of this application and are open-ended and do not exclude the presence of additional elements, materials, components, or method steps that are not described or mentioned. As used herein, “configuration” is understood to exclude the presence of any unspecified elements, components, or method steps in the context of this application. As used herein, “essentially configuration” is understood to include specific elements, materials, components, or method steps of what is described in the context of this application and “that which does not substantially affect the basic and novel properties(s).”

[0277] In this application, unless otherwise specified, the use of the singular form includes the plural form, and the plural form includes the singular form. For example, even if ionic base-containing film-forming polymers, hydroxyl-functional addition polymers, monomers, ionic base-containing film-forming polymers, and blocked polyisocyanate curing agents are mentioned herein, combinations of these components (i.e., plural) may be used. Additionally, in this application, unless otherwise specifically stated, the use of "or" means "and / or," but "and / or" may be explicitly used in certain cases.

[0278] Although specific aspects of the present disclosure have been described in detail, it will be recognized by those skilled in the art that various modifications and alternatives to such details may be developed in light of the entire teaching of the present disclosure. Accordingly, the specific manner disclosed is for illustrative purposes only and is not intended to limit the full scope of the appended claims and the scope of the present disclosure to which any and all equivalents are provided.

[0279] The examples of the present disclosure are the following embodiments, but the details thereof should not be construed as limiting the present disclosure. Unless otherwise indicated, all parts and percentages throughout the specification, as well as in the following embodiments, are by weight.

[0280] Examples

[0281] Example 1: Preparation of blocked polyisocyanate curing agent (crosslinking agents I, Ia-c, II)

[0282] The blocked polyisocyanate curing agent was prepared in the following manner: Components 2–9 listed in Table 1 below were mixed in a flask prepared for total reflux under stirring under nitrogen. The mixture was heated to 30°C, and Component 1 was added dropwise to raise the temperature due to the exothermic reaction, while maintaining the temperature below 100°C. After the addition of Component 1 was completed, Component 10 was added to the mixture. Subsequently, the temperature was established at 100°C and maintained until residual isocyanate was not detected by IR spectroscopy. Then, Component 11 was added, the reaction mixture was stirred for 30 minutes, and cooled to ambient temperature.

[0283] weight part # ingredient I Ia Ib Ic II 1 Polymeric methylene diphenyl diisocyanate 1 1560.9 711.0 785.0 810.0 914.1 2 Dibutyltin dilaurate 1.4 0.9 0.8 0.9 0.9 3 Methyl isobutyl ketone 445.5 270.2 269.7 269.3 154.0 4 Propylene glycol 619.7 - - - - 5 N,N -Dibutylglycolamide - 695.8 - - - 6 N - Butyllactiamide - - 594.3 - - 7 Solketal (DL-1,2-isopropylidene glycerol) - - - 558.4 - 8 (2-(2-butoxyethoxy)ethanol) 566.1 257.2 283.9 293.5 221.0 9 2-Butoxyethanol - - - - 644.0 10 (2-(2-butoxyethoxy)ethanol) 56.9 34.3 34.4 38.2 - 11 Methyl isobutyl ketone 49.5 30.2 30.3 32.2 66.0

[0284] 1 Rubinate M available from Huntsman Corporation

[0285] Example 2: Preparation of Cationic Amine-Functioned Polyepoxide-Based Resin

[0286] Cationic amine-functionalized polyepoxide-based polymeric resins were prepared in the following manner. Components 1-8 listed in Table 2 below were mixed in a flask prepared for total reflux under nitrogen stirring. The mixture was heated to a temperature of 130°C and exothermic (maximum 175°C). After establishing a temperature of 145°C in the reaction mixture, the reaction mixture was maintained for 2 hours. Components 9 were slowly introduced while allowing the mixture to cool to 125°C, followed by the addition of components 10-14. After establishing a temperature of 105°C, components 15 and 16 were rapidly added to the reaction mixture (sequential addition), and the reaction mixture was exothermic. A temperature of 115°C was established, and the reaction mixture was maintained for 1 hour to produce the resin synthesis product AH.

[0287] Subsequently, a portion of the resin synthesis product AH (Component 17) was poured into a pre-mixed solution of Components 18 and 19 to form a resin dispersion, and the resin dispersion was stirred for 30 minutes. Then, Component 20 was introduced over 30 minutes to further dilute the resin dispersion, and then Component 21 was added. The glass MIBK in the resin dispersion was removed from the dispersion under vacuum at a temperature of 60 to 70°C.

[0288] The solid content of the generated cationic amine functionalized polyepoxide-based polymeric resin dispersion was determined by adding a certain amount of the resin dispersion to an aluminum dish weighed by measuring the container weight, recording the initial weight of the resin dispersion, heating the resin dispersion in the dish at 110°C for 60 minutes, cooling the dish to ambient temperature, re-weighing the dish to determine the amount of residual non-volatile content, and calculating the solid content by dividing the weight of the residual non-volatile content by the initial weight of the resin dispersion and multiplying by 100. (Note: This procedure was used to determine the solid content of each resin dispersion example described below). The solid content of the resin dispersion AH is reported in Table 2.

[0289] Suzy Yes: A 3 B C D 4 E F G H # substance Resin synthesis step - parts by weight 1 EPON 828 1 2210.6 863.4 516.1 928.4 363.4 363.1 382.2 896.5 2 Bisphenol A 760.5 284.8 168.4 400.5 125.3 124.9 135.1 309.0 3 Bisphenol A - Ethylene Oxide Adduct (1 / 6 molar ratio BPA / EO) 955.6 416.5 250.0 404.6 188.8 177.2 183.1 404.4 4 phenol 163.3 - - - 26.8 26.8 28.2 66.5 5 4-dodecylphenol - 176.8 - - - - - - 6 12-hydroxystearic acid - - 121.9 - - - - - 7 Methyl isobutyl ketone (MIBK) 126.5 53.5 32.6 53.6 22.2 21.4 22.4 52.1 8 Ethyl triphenyl phosphonium bromide 3.5 1.3 0.8 1.5 0.6 0.6 0.6 1.4 9 Methyl isobutyl ketone 28.1 12.4 7.5 11.7 - - - 69.3 10 Crosslinking agent I 3166.0 1337.4 816.8 1344.2 - - - - 11 Crosslinking agent Ia - - - - 739.0 - - - 12 Crosslinking agent Ib - - - - - 647.5 - - 13 Crosslinking agent Ic - - - - - - 656.8 - 14 Crosslinking agent II - - - - - - - 1342.4 15 Diethylenetriamine - MIBK diketimin 2 203.0 85.4 52.2 86.6 52.3 52.7 55.4 82.0 16 N -methyl ethanolamine 173.4 73.7 44.3 73.1 24.2 24.6 25.9 70.2 17 Resin synthesis product 7011.4 2971.0 1737.6 2967.4 1315.9 1266.1 1307.9 1752.2 18 Pomsan (90% underwater) 98.1 41.5 24.2 41.5 18.2 17.5 18.1 24.5 19 DI number 2734.4 1158.3 674.7 1158.2 491.2 476.0 492.7 682.0 20 DI number 6152.4 2607.0 1519.3 2606.0 1140.5 1099.7 1136.7 1534.7 21 DI number 3199.3 1355.9 789.4 1355.0 592.9 571.9 591.1 798.8 Dispersion solid (wt%) 40.6 37.9 39.6 39.5 38.5 40.5 40.3 39.1

[0290] 1 Diglycidyl ether of bisphenol A having an epoxy equivalent of 186 to 190.

[0291] 2 72.7 wt% of the diketimine reaction product of 1 equivalent of diethylenetriamine and 2 equivalents of MIBK (in MIBK).

[0292] 3 Multiple batches of resin A were manufactured. Their resin solids varied and are further indicated by specific batches in weight percent relative to the total composition weight: resin A1 = 37.70%; A2 = 40.56%; A3 = 39.54%; A4 = 39.94%; A5 = 38.21%; and A6 = 39.76%.

[0293] 4 Multiple batches of resin D were manufactured. Their resin solids varied and are further indicated by specific batches in weight percent relative to the total composition weight: resin D1 = 39.83%; D2 = 36.07%; D3 = 37.63%; D4 = 39.47%; D5 = 36.10%.

[0294] Example 3: Preparation of Polyvinyl Alcohol Solution

[0295] Component 1 was added to a 1 L glass bottle. While stirring the liquid, Component 2 was added over 30 minutes, with 1 / 4 of the substance added every 5 minutes. After stirring for 1 to 3 hours, mixing was stopped, and the solution was heated to 71°C for 16 hours. The solution was cooled to room temperature.

[0296] substance EA 1 EA 3 EA 4 EA 5 EA 6 1 DI number 500 500 500 500 500 2 Hydroxyl functional addition polymer 1 50 - - - - Hydroxyl functional addition polymer 2 - 50 - - - Hydroxyl functional addition polymer 3 - - 50 - - Hydroxyl functional addition polymer 4 - - - 50 - Hydroxyl functional addition polymer 5 - - - - 50

[0297] 1Polyvinyl alcohol polymer having a reported weight average molecular weight of 146,000 to 186,000 g / mol, a reported number average molecular weight of 70,000 to 101,000 g / mol, a reported hydrolysis amount of 88%, and a reported viscosity of 50 ± 5 cP for a 4 wt% aqueous solution at 20°C, measured using a Brookfield synchronous motor rotary type viscometer, commercially available as SELVOL™ 540 of Sekisui Specialty Chemicals America, LLC.

[0298] 2 Polyvinyl alcohol polymer having a reported weight-average molecular weight of 61,600 g / mol, a reported hydrolysis amount of 88%, and a reported viscosity of 3.8 to 4.4 cP for a 4 wt% aqueous solution at 20°C, measured using a commercially available Brookfield synchronous motor rotary type viscometer as Kuraray's Kuraray POVAL™ 4-88.

[0299] 3 A polyvinyl alcohol polymer having a reported weight-average molecular weight of 86,000 g / mol, a reported amount of hydrolysis of 74%, and a reported viscosity of 3.6 to 4.2 cP for a 4 wt% aqueous solution at 20°C, when measured using a commercially available Brookfield synchronous motor rotary type viscometer as Kuraray’s Kuraray POVAL™ 5-74.

[0300] 4 A polyvinyl alcohol polymer having a reported weight-average molecular weight of 214,500 g / mol, a reported amount of hydrolysis of 88%, and a reported viscosity of 20.5 to 24.5 cP for a 4 wt% aqueous solution at 20°C, when measured using a commercially available Brookfield synchronous motor rotary type viscometer as Kuraray’s Kuraray POVAL™ 22-88.

[0301] 5A polyvinyl alcohol polymer having a reported weight-average molecular weight of 310,800 g / mol, a reported amount of hydrolysis of 88%, and a reported viscosity of 90.0 to 120.0 cP for a 4 wt% aqueous solution at 20°C, when measured using a commercially available Brookfield synchronous motor rotary type viscometer as Kuraray’s Kuraray POVAL™ 100-88.

[0302] Example 4: Synthesis of Acrylic Microgel Edge Additive - EA 6

[0303] Injection number substance wealth 1 Product of the example (cationic base-containing polymeric dispersant) 756.80 deionized water 1528.70 2 2-hydroxyethyl acrylate 156.37 3 deionized water 46.35 Hydrogen peroxide (35% of deionized water) 2.37 4 iso-ascorbic acid 0.435 Ammonium iron sulfate 0.0047 deionized water 66.4 5 deionized water 15.65 Hydrogen peroxide (35% of deionized water) 0.068 6 iso-ascorbic acid 0.068 deionized water 15.9

[0304] An aqueous dispersion of Edge Adduct 6 was formed from the components included in the table above. Edge Adduct 6 comprises a cationic polymeric dispersant and an ethylene-based unsaturated monomer composition having 10 wt% of hydroxyl-functional acrylate (2-hydroxyl acrylate) based on the weight of the ethylene-based unsaturated monomer composition. Edge Adduct 6 was prepared as follows: Feed 1 was added to a 4-neck flask equipped with a thermocouple, nitrogen spray, and a mechanical stirrer. Under a nitrogen blanket and vigorous stirring, the flask was heated to 25°C. At 25°C, the solution was further nitrogen-sprayed for 30 minutes. Subsequently, Feed 2 was added to the reaction vessel over 10 minutes. Subsequently, Feed 3 was added to the reaction vessel over 2 to 3 minutes. The components of Feed 4 were mixed together and added to the reactor through an input funnel over 30 minutes. The reaction was exothermic during the addition of feed 4. The reaction became exothermic during the addition. After the addition was completed, the reactor was heated to 50°C and maintained at that temperature for 30 minutes. Feeds 5 and 6 were added dropwise and maintained at 50°C for 30 minutes. Afterward, the reactor was cooled to ambient temperature.

[0305] The solid content of the resulting aqueous dispersion of edge adduct 6 was determined using the method described in Example 2. The measured solid content was 12.33%.

[0306] Weight-average molecular weight (Mw) The z-average molecular weight (Mz) was determined by gel permeation chromatography (GPC). For polymers with a z-average molecular weight of less than 900,000, GPC was performed using a Waters 2695 separation module equipped with a Waters 410 differential refractometer (RI detector), polystyrene standards with a molecular weight of approximately 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 a single Asahipak GF-510 HQ column for separation. With respect to polymers having a z-average molecular weight (Mz) greater than 900,000, GPC is performed using a Waters 2695 separation module equipped with a Waters 410 differential refractometer (RI detector), polystyrene standards having a molecular weight of approximately 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 a single Asahipak GF-7M HQ column for separation. This procedure was performed for all molecular weight measurements included in the examples. It was determined that the comparative edge adduct 2 polymer has a weight-average molecular weight of 404,989 g / mol and a z-average molecular weight of 1,198,186 g / mol.

[0307] Example 5: Preparation of catalyst solution

[0308] An aqueous bismuth methane sulfonate catalyst solution was prepared in the following manner using the components of the table below: Component 1 was added to an Erlenmeyer flask while stirring, and then Components 2 and 3 were introduced sequentially. After stirring the contents of the flask at room temperature for 3 hours, the resulting catalyst solution was filtered through a Buchner funnel to remove any undissolved residues.

[0309] # substance wealth 1 deionized water 2109.7 2 methanesulfonic acid 1 191.9 3 Bismuth(III) oxide 2 288.8

[0310] 1 70% solution in deionized water.

[0311] 2 5N Plus Frit Grade.

[0312] Example 6: Preparation of a quaternary ammonium-containing grind vehicle (Grind Vehicle 1)

[0313] This example describes the preparation of a quaternary ammonium salt containing a pigment grinding resin. Example 6-1 describes the preparation of an amine acid quaternizing agent, and Example 6-2 describes the preparation of an epoxy group-containing polymer subsequently quaternized with the amine acid of Example 6-1.

[0314] Example 6-1 : The amine acid quaternizing agent was prepared using the following procedure:

[0315] # substance wealth 1 dimethyl ethanolamine 445.0 2 PAPI 290 1 661.1 3 Bis[2-(2-butoxyethoxy)ethoxy]methane 2 22.1 4 88% Lactic Acid Water 511.4 5 deionized water 1026.4

[0316] 1 Polymeric diisocyanate commercially available from Dow Chemical Co.

[0317] 2 Available as Mazon 1651 from BASF Corporation

[0318] Component 1 was injected into a suitably fitted 4-neck flask. Subsequently, while maintaining the reaction temperature at ≤100°C, Component 2 was added over a period of 1.5 hours, followed by the addition of Component 3. The resulting mixture was mixed at 90 to 95°C for approximately 1 hour until the reaction of the isocyanate was complete, as determined by infrared spectroscopy. Component 4 and Component 5 were pre-mixed and added over a period of 1 hour. Subsequently, the temperature was established at 85°C, and the mixture was maintained at this temperature for 3 hours to obtain the quaternizing agent for the amine salt.

[0319] Example 6-2 : A quaternary ammonium base-containing polymer was prepared using the following procedure:

[0320] # substance wealth 1 EPON 828 1 568.2 2 Bisphenol A 241.9 3 Bisphenol A - Ethylene Oxide Adduct (1 / 6 molar ratio BPA / EO) 90.0 4 Bis[2-(2-butoxyethoxy)ethoxy]methane 2 9.9 5 Ethyltriphenylphosphonium iodide 0.5 6 Bis[2-(2-butoxyethoxy)ethoxy]methane 2 142.9 7 Bisphenol A diglycidyl ether 1 10.5 8 Bis[2-(2-butoxyethoxy)ethoxy]methane 2 9.0 9 Amine acid quaternizing agent, Example 6-1 314.9 10 deionized water 1731.9

[0321] 1 Diglycidyl ether of bisphenol A having an epoxy equivalent of 186 to 190.

[0322] 2 Available as Mazon 1651 from BASF Corporation

[0323] Components 1-5 were added to a 4-neck flask equipped with a stirrer and a reflux condenser. The reaction mixture was heated to approximately 140°C and then exothermically heated to approximately 180°C. Subsequently, the temperature was established at 160°C, and the mixture was maintained at this temperature for 1 hour to achieve an epoxy equivalent of 900 to 1100 g / equivalent. Component 6 was added, and the temperature was established at 120°C. Then, components 7-8 were added, and the mixture was maintained at 120°C for 1 minute. Subsequently, the temperature was lowered to 90°C. Components 9-10 were pre-mixed and added over a period of 1.5 hours. The reaction temperature was maintained at approximately 80°C for approximately 6 hours until the acid value of the reaction product dropped to less than 1.0, as measured using a Metrohm 799 MPT Titrino automatic titrator utilizing a 0.1 M potassium hydroxide solution in methanol.

[0324] Example 7: Preparation of tertiary sulfonium-containing grind vehicles (grind vehicles 2 and 3)

[0325] # substance wealth Grind Vehicle 2 Grind Vehicle 3 1 EPON 828 1 670.2 150.8 2 nonylphenol 24.0 5.4 3 Bisphenol A 249.7 56.4 4 Ethyltriphenyl phosphonium iodide 0.9 0.2 5 Bis[2-(2-butoxyethoxy)ethoxy]-methane - 55.0 6 Propylene glycol n-butyl ether 243.7 - 7 propylene glycol methyl ether 63.3 - 8 Thiodiethanol 152.8 34.6 9 Propylene glycol n-butyl ether 8.8 14.3 10 deionized water 38.5 28.6 11 dimethylolpropionic acid 167.6 37.9 12 Resin synthesis product 1376.5 383.2 13 deionized water 1339.7 480.8 14 Icomeen T2 2 - 5.8 15 deionized water 750.2 25.5

[0326] 1 Diglycidyl ether of bisphenol A having an epoxy equivalent of 186 to 190.

[0327] 2 Surfactants available from BASF.

[0328] A pulverized carrier was prepared using the materials listed in the table above according to the following procedure: Components 1-6 were poured into a 4-neck flask equipped with a stirrer and a reflux condenser. The mixture was heated to 125°C and exothermically heated to approximately 175°C. A temperature of 160 to 165°C was established, and the mixture was maintained for 1 hour. Component 7 was added, and the temperature was established at 80°C. The mixture of components 8-11 was filled, and the mixture was maintained at 78 to 80°C until the measured acid value was less than 2, as measured using a Metrohm 799 MPT Titrino automatic titrator and a 0.1 M potassium hydroxide solution in a methanol titrator solution. The resulting resin synthesis product, Component 12, was added to Component 13 while stirring. After mixing this dispersion for 30 minutes, Component 14-15 was added to obtain the product.

[0329] Example 8: Preparation of pigment paste

[0330] Catalyst-free pigment dispersions were prepared by sequentially adding the feeds 1-8 listed below under high-shear stirring. Once the components were completely blended, the pigment dispersions were transferred to a vertical sand mill and ground to a Hegman value of >7.5.

[0331] # substance Paste 1 1 Paste 2 Paste 3 Paste 4 1 Grind Vehicle 1 1875.00 750.00 637.5 - Grind Vehicle 2 - - - 1665.26 Grind Vehicle 3 - - - 178.16 2 N-Butoxypropanol 75.32 30.13 25.61 3.94 3 Printex 200 2 28.13 11.25 9.56 24.63 4 ASP 200 3 - 888.75 249.263 947.44 5 titanium dioxide 4 2221.88 - 425.21 328.48 6 Barium sulfate 5 - - 80.96 164.34 7 Bundled 4201 6 - - - 105.31 8 deionized water 799.68 319.87 271.89 584.40

[0332] 1 Paste 1 was prepared three times separately with slightly different solid contents and used to produce compositions having the pigment-to-binder ratio shown below.

[0333] 2 Carbon black pigment supplied by Orion Engineered Carbon

[0334] 3 Kaolin Clay available from BASF Corporation

[0335] 4 Pigment grades originating from The Chemours Company

[0336] 5 Pigment grades of Micro Blanc Fixe

[0337] 6 DBTO available from Arkema, Inc.

[0338] Example 9: Preparation of an electrodepositable coating composition

[0339] For each paint composition described in the table below, fillers 1–5 were sequentially added to a plastic container at room temperature under stirring and stirred for 10 minutes after each addition. This mixture was stirred at room temperature for at least 30 minutes. Subsequently, filler 6 was added and stirred for at least 30 minutes until the paint became homogeneous. Filler 7 was added and stirred for at least 30 minutes until the paint became homogeneous. The resulting cationic electrodeposition paint composition had a solid content of 25% and a pigment-to-binder weight ratio of 0.13 / 1.0, as determined as previously described.

[0340] In addition, comparative compositions for compositions C and G were repeated using the same formulations of compositions C and G, except for the omission of injector 2. These compositions are denoted as C2 and G2.

[0341] After 20% ultrafiltration (and reconstitution with deionized water), the coated panel was prepared from a bath containing a cationic electrodepositable coating composition.

[0342] injection substance A B C D E 1 Suzy A1 - 1218.97 - 1218.97 Suzy A3 - - 1133.02 1138.89 - Suzy B 1211.90 - - - - 2 Bis[2-(2-butoxyethoxy)ethoxy] methane 1 14.29 42.87 57.16 14.29 28.58 3 EA 1 - - 23.81 - - EA 2 - - - - 23.81 EA 6 19.31 19.31 - - 23.81 4 Catalyst solution 5 of the example 47.62 47.62 47.62 47.62 47.62 5 DI number 29.71 22.64 104.10 122.04 18.14 6 Paste 1 135.00 135.00 135.00 135.00 135.00 7 water 792.10 792.10 792.10 792.10 792.10

[0343] 1 Available via Mazon 1651 from BASF (Florham Park, New Jersey).

[0344] injection substance F G H I J 1 Suzy A1 1187.40 - - 　- - Suzy A3 - - - - 748.60 Suzy C - - - 1159.61 - Suji D1 - 1153.79 - - - Suzy D4 - - 1025.56　 -　 - 2 Bis[2-(2-butoxyethoxy)ethoxy] methane 1 14.29 14.29 57.15 14.29 9.44 3 EA 1 - 23.81 　- - 　- EA 2 115.87 - - - - EA 6 - - 115.87 19.42 12.76 4 Catalyst solution 5 of the example 47.62 47.62 47.62 47.62 - 5 DI number 135.48 83.33 81.90 103.21 6 Paste 1 135.00 135.00 92.34 82.16 - Paste 4 - - 230.5 -　 105.00 7 water 714.30 792.10 　- 189.9 521.00

[0345] 1 Available via Mazon 1651 from BASF (Florham Park, New Jersey).

[0346] injection substance K L M N 1 Suzy H 1175.33 - - - Suzy E 1192.41 - - Suzy G 　- - 811.63 - Suzy F - - - 1133.58 2 Bis[2-(2-butoxyethoxy)ethoxy] methane 1 14.29 14.29 12.70 14.29 3 EA 6 19.31 19.31 17.26 19.31 4 Catalyst solution 5 of the example 47.62 47.62 42.33 47.62 5 DI number 66.29 49.21 291.93 108.04 6 Paste 1 135.00 134.50 119.50 134.50 7 water 792.10 720.70 704.60 792.70

[0347] 1 Available via Mazon 1651 from BASF (Florham Park, New Jersey).

[0348] injection substance O Q Q R 1 Suzy A2 - 1133.02 1133.02 1133.02 Suzy A3 1162.25 - - - 2 Bis[2-(2-butoxyethoxy)ethoxy] methane 1 14.29 14.29 14.29 14.29 3 EA 2 23.81 - - - EA 3 - 23.81 - - EA 4 - - 23.81 - EA 5 - - - 23.81 4 Catalyst solution 5 of the example 47.62 47.62 47.62 47.62 5 DI number 74.87 104.1 104.1 104.1 6 Paste 1 134.5 134.5 134.5 134.5 7 water 792.7 792.1 792.7 792.7

[0349] 1 Available via Mazon 1651 from BASF (Florham Park, New Jersey).

[0350] injection substance S T U V 1 Suzy A2 1162.25 - - - Suzy D2 - - 1274.06 - Suzy D3 - 1221.24 - - Suzy D4 - - - 1164.31 2 Bis[2-(2-butoxyethoxy)ethoxy] methane 1 14.29 14.29 14.29 14.29 3 EA 1 - 23.81 - - EA 6 19.31 - 19.31 19.31 4 Catalyst solution 5 of the example 47.62 47.62 47.62 47.62 5 Yttrium solution 2 1.90 1.90 - - DI number 79.37 15.87 5.35 77.31 6 Paste 1 134.5 134.5 135.00 - Paste 2 - - - 149.6 Paste 3 - - - - 7 water 790.80 790.80 754.30 777.60

[0351] 1 Available via Mazon 1651 from BASF (Florham Park, New Jersey).

[0352] 2 Yttrium dissolved in methane sulfonic acid provides 400 ppm yttrium to the resin solid.

[0353] injection substance W X Y z 1 Suzy A5 1202.71 1202.71 1202.71 1202.71 Suzy A6 - - - - 2 Bis[2-(2-butoxyethoxy)ethoxy] methane 1 42.87 28.58 28.58 14.29 3 EA 6 19.31 19.31 19.31 19.31 4 Catalyst solution 5 of the example 47.62 47.62 47.62 47.62 5 DI number 38.91 38.91 38.91 38.91 6 Paste 1 136.4 - 68.20 95.49 Paste 2 - 149.60 74.80 44.87 Paste 3 - - - - 7 water 790.80 777.60 784.20 786.80

[0354] 1 Available via Mazon 1651 from BASF (Florham Park, New Jersey).

[0355] Evaluation of electrodeposition coating compositions

[0356] The paint was evaluated according to the surface roughness test method, edge coverage test method, gelation point method, adhesion temperature test method, and smoothness test method.

[0357] Surface roughness (appearance)Surface roughness can be evaluated according to the Surface Roughness Test Method as follows: After electrodepositing and curing an electrodepositable coating composition onto a metal panel, the coating texture is evaluated using a profilometer over a specified length of the panel and filtered into a roughness profile according to ISO 4287-1997 3.1.6 using an Lc parameter of 2.5 mm and an Ls parameter of 8 μm before summarizing the Ra measurement parameter (hereinafter referred to as Ra) according to ISO 4287-1997 4.2.1. Specific test procedures can be performed as follows: The electrodepositable coating composition can be electrodeposited and coated onto a 4x6x0.032 inch cold-rolled steel (CRS) panel and pretreated with CHEMFOS C700 / DI (CHEMFOS C700 is a zinc phosphate immersion pretreatment composition available from PPG Industries, Inc.). These panels are available from ACT Laboratories in Hillside, Michigan. The electrodepositable paint composition described above was electrodeposited onto a specially manufactured panel in a manner well known in the art by immersing the panel in a stirring bath at a temperature of 32.2°C to 37.2°C, connecting the cathode of a DC rectifier to the panel, and connecting the anode of the DC rectifier to stainless steel tubing used to circulate cooling water for bath temperature control. The voltage was increased from 0 to a set point of 190 V over a period of 30 seconds and maintained at that voltage until the desired film thickness was achieved. This combination of time, temperature, and voltage deposited a coating having a dry film thickness of 16 to 20 microns when cured. Three panels were electrocoated for each paint composition. After electrodeposition, the panel was removed from the bath, vigorously rinsed with a spray of deionized water, and cured by firing in an electric oven (Despatch Industries, model LFD series) at 150°C for 20 minutes.

[0358] The texture of the coated panel can be evaluated using a Mitutoyo Surftest SJ-402 skid stylus profilometer equipped with a 0.75 mN detector and a diamond stylus tip having a 60° cone and a 2 μm tip radius. The scan force is less than 400 mN. The scan length, measurement speed, and data sampling interval were 15 mm, 0.5 mm / s, and 1.5 μm, respectively. First, the raw data was filtered into a roughness profile according to ISO 4287-1997 3.1.6 using an Lc parameter of 2.5 mm and an Ls parameter of 8 μm, before summarizing the Ra measurement (hereinafter referred to as Ra (2.5 mm)) according to ISO 4287-1997 4.2.1.

[0359] Edge coverage evaluation Edge coverage can be evaluated by the following methods according to the edge coverage test method: Test The panel was specially manufactured from a 4 x 12 x 0.032 inch cold-rolled steel panel, pretreated with CHEMFOS C700 / DI and available from ACT Laboratories in Hillsdale, Michigan. First, a 4 x 12 x 0.32 inch panel was cut into two 4 x 5-3 / 4 inch panels using Di-Acro Hand Shear No. 24 (DiAcro, Oak Park Heights, Minnesota). The panel was positioned on the cutter so that the burr edge from the cut along the 4-inch edge stopped on the side facing the top surface of the panel. Next, each 4 x 5-3 / 4 panel was positioned on the cutter to remove ¼ inch from one of the 5-3 / 4-inch sides of the panel in such a way that the burr obtained from the cut faced upward toward the top surface of the panel.

[0360] Subsequently, the electrodepositable paint composition described above was immersed in a stirring bath at 32.2°C to 37.2°C, the cathode of a DC rectifier was connected to the panel, and the anode of the DC rectifier was connected to stainless steel tubing used to circulate cooling water for bath temperature control, and electrodeposited onto this specially manufactured panel in a manner well known in the art. The voltage was increased from 0 to a set point of 190V over a period of 30 seconds and maintained at that voltage until the desired film thickness was achieved. This combination of time, temperature, and voltage deposited a coating having a dry film thickness of 16 to 20 microns when cured. Two panels were electrocoated with their respective paint compositions. After electrodeposition, the panels were removed from the bath, vigorously rinsed with a spray of deionized water, and cured by firing in an electric oven at 150°C for 20 minutes.

[0361] Using a Di-Acro panel cutter (model number 12 SHEAR), a square piece approximately 0.5 inches x 0.5 inches was cut from the burr edge of the panel. The burr edge is placed inside an epoxy cup, with 10 burrs per epoxy mount. This is done using Ted Pella plastic multi-clips. Leco epoxy (811-563-101) and Leco hardener (812-518) are mixed in a 100:14 ratio and poured into the mounting cup containing the burr specimens. The epoxy is allowed to cure overnight. Afterward, the epoxy mounts are ground and polished using a Buehler AutoMet 250. First, 240 grit paper is used for 2 minutes and 30 seconds. Then, 320 grit paper is used for 2 minutes. Finally, 600 grit paper is used for 1 minute. Subsequently, the sample is polished for 3 minutes and 30 seconds using 9-micron paste, followed by polishing for 3 minutes using 3-micron paste. Once polished, the sample is coated with Au / Pd for 20 seconds using an EMS Quorum EMS150TES Sputter Coater and placed on an aluminum mount with carbon tape. The coating thickness of the burr was evaluated and compared with the coating thickness of the flat area.

[0362] Gel point evaluationThe gel point can be evaluated according to the Gel Point Test Method as follows: The electrodepositable coating composition is coated onto a 4" x 12" .025" aluminum Q panel available from OH Westlake Q-Labs until a target film of 0.7 to 0.9 mils (17 to 23 microns) is reached. Subsequently, the applied uncured coating is dissolved in THF, deposited onto a Type P-PTD200 / 56 platen, and placed on an Anton Paar hardness tester (Model 302) using an Anton Paar PPR 25 / 23 spindle with a constant 5% shear strain and a constant 1 Hz frequency setting. The temperature is maintained at 40°C for 30 minutes, then increased from 40°C to 175°C at a rate of 3.3°C / min. Complex viscosity (cps, η*), shear strain (%, γ), and loss The modulus (G” / G’), loss modulus (Pa, G”), storage modulus (Pa, G’), and shear stress (Pa, τ) are measured over a temperature gradient, and the gelation point is determined as the point where the loss modulus (G”) intersects the storage modulus (G’).

[0363] Adhesion temperature evaluation : The adhesion temperature can be evaluated according to the adhesion temperature test method by the following method: An electrodepositable coating composition is coated onto a test panel, e.g., a 4 x 6 x 0.031 inch cold-rolled steel (CRS) panel pretreated with CHEMFOS C700 / DI (CHEMFOS C700 is a zinc phosphate immersion pretreatment composition available from PPG Industries, Inc.). Panels are available from ACT Laboratories in Hillside, Michigan. The panel is coated using a voltage of 190 V and an immersion time of 3 minutes. 70 to 3℉ intervals Electrocoating is performed at an electrodeposition bath temperature of 102℉ (maximum 102℉). Subsequently, the panel is fired at 150℃ for 20 minutes. Film formation is measured using a Fischer Dualscope FMP40 permascope instrument. If a minimum film formation value is identified within the tested temperature range, the temperature at which the lowest film formation is measured is designated as the adhesion temperature of the electrodepositable coating composition.

[0364] Smoothness % Smoothness % can be evaluated according to the smoothness test method as follows: A 4x6x0.031 inch cold-rolled steel (CRS) panel available from ACT Laboratories in Hillside, Michigan, pretreated with CHEMFOS C700 / DI (CHEMFOS C700 is a zinc phosphate immersion pretreatment composition available from PPG Industries, Inc.) is used for this evaluation. This substrate typically has an Ra of 0.6 (2.5 mm). The surface roughness of the uncoated panel was evaluated using a Mitutoyo Surftest SJ-402 skid dress stylus profilometer equipped with a 4 mN detector and a diamond stylus tip having a 90° cone and a 5 μm tip radius. The scan length, measurement speed, and data sampling interval were 48 mm, 1 mm / s, and 5 μm, respectively. Subsequently, the sampling data is transmitted to a personal computer using a USB port located on the profilometer, and first, the raw data is filtered into a roughness profile according to ISO 4287-1997 3.1.6 using an Lc parameter of 2.5 mm and an Ls parameter of 8 μm before summarizing the Ra measurement item (hereinafter referred to as Ra (2.5 mm)) according to ISO 4287-1997 4.2.1.

[0365] The test results are provided in the table below.

[0366] paint single reactants CAT EA Ra(2.5mm) Smoothness Burr CT GP A DDP Bi-MSA EA 6 0.344 43% 21% 78 136 B phenol Bi-MSA EA 6 0.228 62% 41% 72 136 C phenol Bi-MSA EA 1 0.450 25% 24% 75 138 Composition G doesn't exist Bi-MSA EA 1 0.873 -46% 28% 72 127 I HSA* Bi-MSA EA 6 0.267 56% 22% 72 137

[0367] *HSA - 12-hydroxystearic acid

[0368] The results shown above demonstrate that using a monofunctional reactant in the preparation of electrodeposited binder resins produces good curing performance and appearance compared to similar electrodeposited coating compositions that do not contain a monofunctional reactant in the preparation of the resin. For example, Composition C, which contains phenol as a monofunctional reactant and EA 1 as an edge adduct, shows significantly reduced surface roughness and a smoother surface compared to Comparative Composition G, which has the same edge adduct but lacks a monofunctional reactant. Similarly, Compositions A, B, and I also contain a monofunctional reactant and provided good appearance, smoothness, and edge coverage.

[0369] paint single reactants CAT EA Ra(2.5mm) Smoothness Burr CT GP A DDP Bi-MSA EA 6 0.344 43% 21% 78 136 B phenol Bi-MSA EA 6 0.228 62% 41% 72 136 C phenol Bi-MSA EA 1 0.450 25% 24% 75 138 Composition D phenol Bi-MSA doesn't exist 0.159 74% 2% 72 137 E phenol Bi-MSA EA 2 0.321 47% 2% 72 135 Composition G doesn't exist Bi-MSA EA 1 0.873 -46% 28% 72 127 Composition H doesn't exist Bi-MSA EA 6 3.638 -506% 152% 72 131

[0370] The results in the table above demonstrate that using various edge add-ons can increase the edge coverage of electrodeposited coating compositions while providing good appearance and low-temperature curing. For example, compositions A, B, and C all provide excellent appearance, edge coverage, smoothness, adhesion, and gelation point. In contrast, comparative composition D did not contain edge add-ons and provided poor edge coverage.

[0371] In addition, the results in the table above demonstrate that using a monofunctional reactant can help improve the appearance while maintaining edge coverage. For example, composition B can be compared with comparative composition H, which does not contain a monofunctional reactant during resin preparation and has a composition with significant edge coverage, producing a very rough surface.

[0372] paint single reactants CAT EA Ra(2.5mm) Smoothness CT GP C phenol Bi-MSA EA 1 0.450 25% 75 138 G doesn't exist Bi-MSA EA 1 0.873 -46% 72 127 C2 phenol Bi-MSA EA 1 0.513 14% 85 137 G2 doesn't exist Bi-MSA EA 1 2.079 -246% 91 129

[0373] These results demonstrate that the bonding temperature can be reduced by including 0.8 wt% of bis[2-(2-butoxyethoxy)ethoxy]-methane based on the resin solid, and that the use of a monofunctional reactant can also affect the bonding temperature (comparing Composition C2 and Composition G2, which show a reduced CT for the resin containing the monofunctional reactant of Composition C2).

[0374] paint single reactants CAT EA Ra(2.5mm) Smoothness Burr CT GP A DDP Bi-MSA EA 6 0.344 43% 21% 78 136 J phenol DBTO EA 6 0.435 28% 20% 72 137

[0375] The results in the table above demonstrate that different catalysts can be used to achieve appearance, smoothness, edge coverage, adhesion temperature, and gelation point.

[0376] paint single reactants EA Ra(2.5mm) Smoothness Burr CT GP Composition K phenol EA 6 0.110 87% 21% 72 166 L phenol EA 6 0.381 37% 41% 72 118 M phenol EA 6 0.410 32% 24% 72 148 N phenol EA 6 0.240 60% 21% 75 134

[0377] Catalyst Bi-MSA - All

[0378] These results in the table above indicate that the blocking agent used to form the crosslinking agent blocker can affect the gelation point temperature of the composition. For example, Comparative Composition K, which had a polyisocyanate blocked by butyl cellosolve, had a significantly higher gelation point than Compositions L, M, and N, which used different blocking agents.

[0379] paint single reactants pigment EA Ra(2.5mm) Smoothness Burr GP U doesn't exist 100% TiO2 EA 6 0.415 31% 6% 132 Composition V doesn't exist 100% clay EA 6 0.623 -4% 14% 155 W phenol 100% TiO2 EA 6 0.256 57% 20% 139 X phenol 100% clay EA 6 0.446 26% 33% 135 Y phenol 50:50(TiO2:clay) EA 6 0.439 27% 16% 137 z phenol 70:30(TiO2:clay) EA 6 0.434 28% 46% 137

[0380] The results in the table above indicate that when resins are not prepared using monofunctional reactants, the curing temperature may vary depending on the type of pigment used. For example, Composition U, containing 100% TiO2 pigment, had a lower gelation point compared to Comparative Composition V, which contained 100% clay pigment and had a higher gelation point. Additionally, clay affected edge coverage, as in Compositions V and Y. Compositions V and Y had poorer edge coverage because clay was present in amounts of 100 wt% and 50 wt%, respectively, based on the total pigment weight. Composition Z, which contained only 30 wt% clay, exhibited good gelation point and edge coverage. Furthermore, the results indicate that pigments can be changed more freely when resins are prepared using monofunctional reactants. For example, Compositions W, Y, X, and Z all contain a monofunctional reactant (phenol) and utilize resins that maintain a low gelation point regardless of the pigment used.

[0381] paint single reactants additives EA Ra(2.5mm) Smoothness Burr CT GP S phenol yttrium EA 6 0.294 51% 52% 72 148 T doesn't exist yttrium EA 6 0.434 28% 19% 72 151

[0382] The results in the table above indicate that corrosion inhibitors such as yttrium can be incorporated into electrodeposited coating compositions without destroying the properties of the composition.

[0383] paint single reactants pigment EA Ra(2.5mm) Smoothness Burr O phenol 100% TiO2 EA 2 0.150 75% 0% P phenol 100% TiO2 EA 3 0.156 74% 0% Q phenol 100% TiO2 EA 4 0.206 66% 24% R phenol 100% TiO2 EA 5 0.279 54% 40%

[0384] The results indicate, for example, that multiple different types of hydroxyl-functional additives can be incorporated into the electrodeposited coating composition. In particular, hydroxyl-functional additive polymers with higher molecular weights provided better edge coverage than edge additives with lower molecular weights. For example, EA 2 and EA 3 have lower molecular weights, while EA 4 and EA 5 have higher molecular weights. However, each provides good appearance and smoothness.

[0385] A person skilled in the art will recognize that numerous variations and modifications are possible in light of the foregoing disclosures without departing from the broad concept of the invention described and illustrated herein. Accordingly, it should be understood that the foregoing disclosures merely illustrate various exemplary aspects of this application, and that numerous variations and modifications can be readily made by a person skilled in the art within the spirit and scope of this application and the appended claims.

Claims

Claim 1 An electrodepositable coating composition comprising: (a) an active hydrogen-containing ionic base-containing film-forming polymer; (b) a blocked polyisocyanate curing agent; (c) a curing catalyst; and (d) an edge control adduct; wherein the electrodepositable coating composition has a gel point of less than 150°C when measured by a gel point test method, an edge coverage of more than 20% when measured by an edge coverage test method, and an Ra of 0.45 or less when measured by a surface roughness test method. Claim 2 A electrodepositable coating composition according to claim 1, wherein the ionic base-containing film-forming polymer comprises a reaction product of a reaction mixture comprising (1) a polyepoxide; (2) a difunctional chain extender; and (3) a monofunctional reactant, and the ratio of the functional groups of the difunctional chain extender and the monofunctional reactant to the epoxide functional groups of the polyepoxide may be 0.50:1 to 0.85:

1. Claim 3 delete Claim 4 In paragraph 2, the reaction product is an electrodepositable coating composition having an epoxy equivalent of 700 to 1,500 g / equivalent. Claim 5 The electrodepositable coating composition according to claim 1, wherein the electrodepositable coating composition has a adhesion temperature of less than 90℉ when measured by the adhesion temperature test method. Claim 6 An electrodepositable coating composition comprising: (a) an active hydrogen-containing ionic base-containing film-forming polymer comprising a reaction product of a reaction mixture comprising (1) a polyepoxide; (2) a difunctional chain extender; and (3) a monofunctional reactant; (b) a blocked polyisocyanate curing agent; (c) a curing catalyst; and (d) an edge control adduct; wherein the electrodepositable coating composition has a gelation point of less than 150°C when measured by a gelation point test method and an adhesion temperature of less than 90°F when measured by an adhesion temperature test method. Claim 7 delete Claim 8 delete Claim 9 The electrodepositable coating composition according to claim 1, wherein the blocked polyisocyanate curing agent comprises a blocker comprising a 1,2-polyol as a blocking agent. Claim 10 delete Claim 11 delete Claim 12 delete Claim 13 delete Claim 14 In claim 9, the electrodepositable coating composition wherein the 1,2-polyol comprises propylene glycol. Claim 15 delete Claim 16 delete Claim 17 delete Claim 18 delete Claim 19 The electrodepositable coating composition according to claim 1, wherein the blocked polyisocyanate curing agent comprises a blocker derived from a blocker comprising an alpha-hydroxyamide, ester, or thioester. Claim 20 delete Claim 21 In claim 19, the electrodepositable coating composition comprises an alpha-hydroxyamide blocker comprising an alkyl glycolamide and / or alkyl lactamide. Claim 22 delete Claim 23 delete Claim 24 delete Claim 25 delete Claim 26 delete Claim 27 delete Claim 28 delete Claim 29 In claim 1, the curing catalyst comprises guanidine, forming an electrodepositable coating composition. Claim 30 delete Claim 31 The electrodepositable coating composition according to claim 1, wherein the curing catalyst comprises a bismuth catalyst and / or a zinc-containing catalyst. Claim 32 The electrodepositable coating composition according to claim 1, wherein the curing catalyst comprises a bismuth catalyst. Claim 33 In paragraph 32, the above curing catalyst further comprises guanidine, forming an electrodepositable coating composition. Claim 34 delete Claim 35 In claim 1, the electrodepositable coating composition comprises an active hydrogen-containing ionic base-containing film-forming polymer, wherein the active hydrogen-containing ionic base-containing film-forming polymer comprises an active hydrogen-containing cation-containing film-forming polymer. Claim 36 In claim 1, the electrodepositable coating composition comprises an active hydrogen-containing anionic base-containing film-forming polymer, wherein the active hydrogen-containing anionic base-containing film-forming polymer comprises an active hydrogen-containing anionic base-containing film-forming polymer. Claim 37 delete Claim 38 delete Claim 39 In claim 1, the edge control adduct comprises: (1) an addition polymer comprising a polymerization product of a polymeric dispersant and a second-stage ethylene-based unsaturated monomer composition comprising a second-stage hydroxyl-functional (meth)acrylamide monomer and / or a second-stage hydroxyl-functional (meth)acrylate monomer; (2) a hydroxyl-functional addition polymer comprising a constituent unit, wherein at least 70% is of Formula VIII: ―[―C(R 1 )2―C(R 1 )(OH)―]― (VIII), including each R 1 is independently one of hydrogen, an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an alkylcycloalkyl group, a substituted alkylcycloalkyl group, a cycloalkylalkyl group, a substituted cycloalkylalkyl group, an aryl group, a substituted aryl group, an alkylaryl group, a substituted alkylaryl group, a cycloalkylaryl group, a substituted cycloalkylaryl group, an arylalkyl group, a substituted arylalkyl group, an arylcycloalkyl group, or a substituted arylcycloalkyl group, wherein the % is based on the total constituent unit of the hydroxyl-functional addition polymer, and the R 1 A electrodepositable coating composition comprising a hydroxyl-functional addition polymer, wherein the substituents in each are independently selected from a halogen atom; a nitrile group; a nitro group; a partial or complete alkyl halide, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl and arylcycloalkyl radical; an aryloxy, alkyloxy and cycloalkyloxy radical; an arylthio, alkylthio and cycloalkylthio radical; a hydroxyl group; and primary, secondary and tertiary amino groups; (3) a cellulose derivative; (4) a polyvinyl formamide; (5) a cationic epoxy microgel; (6) a polyamine-dialdehyde adduct or any combination thereof. Claim 40 The electrodepositable coating composition according to claim 1, wherein the electrodepositable coating composition has a smoothness % of at least 30% when measured by a smoothing test method. Claim 41 The electrodepositable coating composition according to claim 1, further comprising bis[2-(2-butoxyethoxy)ethoxy]methane. Claim 42 A method for coating a substrate, comprising the step of electrophoretically applying a coating deposited from the electrodepositable coating composition of claim 1 to at least a portion of the substrate. Claim 43 delete Claim 44 delete Claim 45 delete Claim 46 delete Claim 47 delete Claim 48 delete Claim 49 A coated substrate comprising a coating formed by electrodepositing an electrodepositable coating composition according to claim 1 onto a substrate and curing the coating at least partially. Claim 50 delete Claim 51 delete Claim 52 delete

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