Electrodeposition coating film having multiple resin domains

Abstract

The present disclosure relates to an electrodeposited coating, or a coated metal substrate comprising an electrodeposited coating, the electrodeposited coating comprising a platelet-like pigment present in a pigment-to-binder ratio of at least 0.4:1 and an electrodeposited binder comprising first resin domains having a first glass transition temperature and a second resin domain having a second glass transition temperature, the first glass transition temperature being at least 10° C. higher than the second glass transition temperature and the second glass transition temperature being greater than −50° C., and / or the first glass transition temperature being at least 80° C. and the second glass transition temperature being between −50° C. and 70° C. Also disclosed are electrodepositable coating compositions and methods of coating a substrate.

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE The present disclosure relates to electrodepositable coating compositions, electrodeposited coatings, coated substrates, and methods of coating substrates. [Background technology]

[0002] Electrodeposition as a coating method involves depositing a film-forming composition onto a conductive substrate under the influence of an applied electric potential. Electrodeposition has gained widespread acceptance in the coatings industry due to its increased paint use efficiency, superior corrosion resistance, and reduced environmental pollution compared to non-electrodeposition coating methods. Both cationic and anionic electrodeposition processes are used commercially. Summary of the Invention

[0003] The present disclosure provides an electrodeposition coating, or a coated conductive substrate comprising an electrodeposition coating, the electrodeposition coating comprising a platelet-like pigment present in a pigment to binder ratio of at least 0.4:1, and an electrodeposited binder comprising first resin domains having a first glass transition temperature and a second resin domain having a second glass transition temperature, wherein the first glass transition temperature is at least 10°C higher than the second glass transition temperature, such as at least 20°C, for example at least 30°C, such as at least 40°C, for example at least 50°C, such as at least 60°C, for example at least 70°C, for example at least 80°C, for example at least 90°C, such as at least 100°C, for example at least 110°C, such as at least 120°C, for example at least 130°C, such as at least 140°C, for example at least 150°C, for example at least 160°C, for example at least 170°C, and wherein the second glass transition temperature is higher than -50°C.

[0004] The present disclosure also provides an electrodeposited coating, or a coated conductive substrate comprising an electrodeposited coating, the electrodeposited coating comprising a platelet-like pigment present in a pigment-to-binder ratio of at least 0.4:1, and an electrodeposited binder comprising a first resin domain having a first glass transition temperature of at least 80°C and a second resin domain having a second glass transition temperature of -50°C to 70°C.

[0005] The present disclosure further provides an electrodepositable coating composition comprising an electrodepositable binder comprising an active hydrogen-containing, ionic salt group-containing film forming polymer, a curing agent, and at least one organic resin component different from the active hydrogen-containing, ionic salt group-containing film forming polymer and the curing agent; and a platelet-like pigment present in a pigment-to-binder ratio of at least 0.4:1.

[0006] The present disclosure also provides a method of coating a substrate, comprising electrophoretically applying to at least a portion of the substrate a coating deposited from an electrodepositable coating composition, the electrodepositable coating composition comprising an electrodepositable binder comprising an active hydrogen-containing, ionic salt group-containing film forming polymer, a curing agent, at least one organic resin component different from the active hydrogen-containing, ionic salt group-containing film forming polymer and the curing agent, and a platelet-like pigment present in a pigment-to-binder ratio of at least 0.4:1. [Brief explanation of the drawings]

[0007] [Figure 1] 1 is a compilation of TEM images of the electrodeposition coating films described in Examples 1 to 5. DETAILED DESCRIPTION OF THE INVENTION

[0008] The present disclosure relates to an electrodeposited coating, or a coated conductive substrate comprising an electrodeposited coating, the electrodeposited coating comprising a platelet-like pigment present in a pigment to binder ratio of at least 0.4:1, and an electrodeposited binder comprising first resin domains having a first glass transition temperature and a second resin domain having a second glass transition temperature, wherein the first glass transition temperature is at least 10°C higher than the second glass transition temperature, such as at least 20°C, for example at least 30°C, such as at least 40°C, for example at least 50°C, such as at least 60°C, for example at least 70°C, for example at least 80°C, for example at least 90°C, such as at least 100°C, for example at least 110°C, such as at least 120°C, for example at least 130°C, such as at least 140°C, for example at least 150°C, for example at least 160°C, for example at least 170°C, and wherein the second glass transition temperature is higher than -50°C.

[0009] The present disclosure also relates to an electrodeposited coating, or a coated conductive substrate comprising an electrodeposited coating, the electrodeposited coating comprising a platelet-like pigment present in a pigment-to-binder ratio of at least 0.4:1 and an electrodeposited binder comprising a first resin domain having a first glass transition temperature of at least 80°C and a second resin domain having a second glass transition temperature of -50°C to 70°C.

[0010] The present disclosure also relates to an electrodepositable coating composition comprising an electrodepositable binder comprising an active hydrogen-containing, ionic salt group-containing film-forming polymer, a curing agent, and at least one organic resin component different from the active hydrogen-containing, ionic salt group-containing film-forming polymer and the curing agent; and a platelet-like pigment present in a pigment-to-binder ratio of at least 0.4:1.

[0011] Plate-shaped pigment The electrodeposited coating and / or electrodepositable coating composition comprises a platelet-like pigment present in a pigment to binder ratio of at least 0.4:1.

[0012] The plate-like pigment may be an inorganic plate-like pigment.

[0013] The platelet pigment may be a phyllosilicate pigment. As used herein, the term "phyllosilicate" refers to a group of minerals having a silicate sheet structure, the basic structure of which is SiO -4 The six-membered rings of tetrahedrons are interconnected to form an infinitely expanding sheet, with each tetrahedron sharing three of its four oxygen atoms with other tetrahedra. As a result, phyllosilicates are made up of SiO5 -2 The phyllosilicates may contain hydroxide ions located at the center of the tetrahedron and / or may contain, for example, Fe +2 , Mg +2 , or Al +3 These cations may form cationic layers between the silicate sheets, where they may coordinate with oxygen and / or hydroxide ions in the silicate layers. The term "phyllosilicate pigment" refers to a pigment material comprising a phyllosilicate. Non-limiting examples of phyllosilicate pigments include mica, chlorite, serpentine, talc, and clay minerals. Clay minerals include, for example, kaolin clay and smectite clay. The sheet-like structure of phyllosilicate pigments tends to result in pigments having a plate-like structure, although pigments can be processed (e.g., by mechanical means) to have other particle structures. These pigments may or may not swell when exposed to a liquid medium and may or may not contain leachable components (e.g., ions that are attracted to the liquid medium).

[0014] The platelet pigments may include platelet mica pigments, platelet chlorite pigments, platelet serpentine pigments, platelet talc pigments, and / or platelet clay pigments. The platelet clay pigments may include kaolin clays, smectite clays, or combinations thereof.

[0015] The pigment component includes platelet-like pigments having an average equivalent spherical diameter of at least 50 nm and can be as large as 25 microns or more. The average equivalent spherical diameter may be determined by dynamic light scattering, such as with a Micromeritics Instrument SEDIGRAPH III PLUS particle size analyzer. As platelet-like particles, pigments often have substantially opposed surfaces, and the particles typically have an aspect ratio of the longest axis to the shortest axis of, for example, at least 2:1. For example, the platelet-like pigments may have an average equivalent spherical diameter of at least 50 nm, such as at least 0.2 microns, such as at least 0.4 microns, such as at least 0.6 microns, such as at least 1 micron, such as at least 2 microns, such as at least 3 microns, such as at least 4 microns, such as at least 5 microns. The platelet-like pigments may have an average equivalent spherical diameter of 25 microns or less, such as 15 microns or less, such as 10 microns or less, such as 5 microns or less, such as 3.5 microns or less, such as 2.5 microns or less, such as 1.9 microns or less, such as 1.5 microns or less, such as 1 micron or less.

[0016] The pigment-to-binder (P:B) ratio defined in this 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 (i.e., electrodeposited coating). The pigment to electrodepositable binder (P:B) ratio may be at least 0.4:1, such as at least 0.5:1, such as at least 0.6:1, such as at least 0.75:1, such as at least 1:1, such as at least 1.25:1, such as at least 1.5:1. The pigment to binder (P:B) ratio, which is the ratio of pigment to electrodepositable or electrodeposited binder, may be 2:1 or less, such as 1.75:1 or less, such as 1.5:1 or less, such as 1.25:1 or less, such as 1:1 or less, such as 0.75:1 or less, such as 0.7:1 or less, such as 0.6:1 or less, such as 0.55:1 or less, such as 0.5:1 or less.The pigment to binder (P:B) ratio, which is the ratio of pigment to electrodepositable or electrodeposited binder, may be from 0.4:1 to 2:1, such as from 0.4:1 to 1.75:1, for example from 0.4:1 to 1.5:1, for example from 0.4:1 to 1.25:1, for example from 0.4:1 to 1:1, for example from 0.4:1 to 0.75:1, for example from 0.4:1 to 0.7:1, for example from 0.4:1 to 0. .6:1, for example 0.4:1~0.55:1, for example 0.4:1~0.5:1, for example 0.5:1~2:1, for example 0.5:1~1.75:1, for example 0.5:1~1.50:1, for example 0.5:1~1.25:1, for example 0.5:1~1:1, for example 0.5:1~0.75:1, for example 0.5:1~0.7:1, for example 0.5:1~0.6:1, for example 0.5: 1 to 0.55:1, for example 0.6:1 to 2:1, for example 0.6:1 to 1.75:1, for example 0.6:1 to 1.5:1, for example 0.6:1 to 1.25:1, for example 0.6:1 to 1:1, for example 0.6:1 to 0.75:1, for example 0.6:1 to 0.7:1, for example 0.75:1 to 2:1, for example 0.75:1 to 1.75:1, for example 0.75:1 to 1.5:1, It may be for example 0.75:1 to 1.25:1, for example 0.75:1 to 1:1, for example 1:1 to 2:1, for example 1:1 to 1.75:1, for example 1:1 to 1.5:1, for example 1:1 to 1.25:1, for example 1.25:1 to 2:1, for example 1.25:1 to 1.75:1, for example 1.25:1 to 1.5:1, for example 1.5:1 to 2:1, for example 1.5:1 to 1.75:1.

[0017] Resin Domain As used herein, the term "resin domain" in a first resin domain or a second resin domain refers to a visible disruption in the homogeneity of the binder. The visible disruption may be visible using TEM and / or SEM. For example, the first resin domain may be a bulk resin, and the second resin domain may exist as a resin region phase-separated from the bulk resin. For example, the second resin domain may be dispersed pockets of resin dispersed throughout the bulk resin of the first resin domain. The dispersed pockets of resin may have any geometric shape or morphology, such as, for example, spherical, lamellar, or cylindrical. The dispersed pockets may be generally uniformly dispersed or non-uniformly dispersed. The dispersed pockets may be distributed in layers throughout the bulk resin. Alternatively, the first and second resin domains may be phase-separated into a two-layer configuration, with one resin domain present at the surface of the substrate and the other resin domain present on top of it. The resin domains may be substantially free of platelet pigments.

[0018] As mentioned above, visible disturbances may be visible using TEM. Identification of secondary resin domains may be determined according to the following method, referred to herein as TEM analysis: Coated and cured panels are cut to size, embedded in EMBed-812 epoxy resin, and cured at 60°C for 24 hours. Thin sections (<80 nm) are then sectioned using an ultrathin microtome and collected on copper TEM grids. Bright-field images are taken using a Tecnai T20 TEM operating at 200 kV. Visible resin domains may be identified in the resulting TEM images. Further image analysis can be performed to determine the size of the resin domains, as described in the Examples section below.

[0019] The first resin domain has a first glass transition temperature and the second resin domain has a second glass transition temperature, which may be at least 10°C higher than the second glass transition temperature, such as at least 20°C, for example at least 30°C, such as at least 40°C, for example at least 50°C, such as at least 60°C, for example at least 70°C, such as at least 80°C, for example at least 90°C, such as at least 100°C, for example at least 110°C, such as at least 120°C, for example at least 130°C, such as at least 140°C, for example at least 150°C, such as at least 160°C, for example at least 170°C, and the second glass transition temperature is higher than -50°C.

[0020] The first glass transition temperature may be at least 80° C., such as at least 90° C., for example at least 100° C., such as at least 110° C., for example at least 120° C., such as at least 125° C. The first glass transition temperature may be 130° C. or less, such as 120° C. or less, such as 110° C. or less, such as 100° C. or less, for example 90° C. or less. The first glass transition temperature may be 80°C to 130°C, for example, 80°C to 120°C, for example, 80°C to 110°C, for example, 80°C to 100°C, for example, 80°C to 90°C, for example, 90°C to 130°C, for example, 90°C to 120°C, for example, 90°C to 110°C, for example, 90°C to 100°C, for example, 100°C to 130°C, for example, 100°C to 120°C, for example, 100°C to 110°C, for example, 110°C to 130°C, for example, 110°C to 120°C, for example, 120°C to 130°C.

[0021] The second glass transition temperature may be at least −50° C., such as at least −40° C., for example at least −30° C., such as at least −20° C., for example at least −10° C., such as at least 0° C., for example at least 10° C., such as at least 20° C., for example at least 30° C., such as at least 40° C., for example at least 50° C., for example at least 60° C. The second glass transition temperature may be 70° C. or lower, such as 50° C. or lower, for example 30° C. or lower, for example 10° C. or lower, such as 0° C. or lower, for example −10° C. or lower, for example −20° C. or lower, for example −30° C. or lower. The second glass transition temperature may be -50°C to 70°C, for example -50°C to 50°C, for example -50°C to 30°C, for example -50°C to 10°C, for example -50°C to 0°C, for example -50°C to -10°C, for example -50°C to -20°C, for example -50°C to -30°C, for example -40°C to 70°C, for example -40°C to 50°C, for example -40°C to 30°C, for example -40℃ to 10℃, for example -40℃ to 0℃, for example -40℃ to -10℃, for example -40℃ to -20℃, for example -40℃ to -30℃, for example -30℃ to 70℃, for example -30℃ to 50℃, for example -30℃ to 30℃, for example -30℃ to 10℃, for example -30℃ to 0℃, for example -30℃ to -10℃, for example -30℃ to -20℃, for example -20℃ to 70°C, for example, -20°C to 50°C, for example, -20°C to 30°C, for example, -20°C to 10°C, for example, -20°C to 0°C, for example, -20°C to -10°C, for example, -10°C to 70°C, for example, -10°C to 50°C, for example, -10°C to 30°C, for example, -10°C to 10°C, for example, -10°C to 0°C, for example, 0°C to 70°C, for example, 0°C to 50°C, for example, 0°C to 30°C, for example, 0°C to 10°C, for example, 10°C to 70°C, for example, 10°C to 50°C, for example, 10°C to 30°C, for example, 20°C to 70°C, for example, 20°C to 50°C, for example, 20°C to 30°C, for example, 30°C to 70°C, for example, 30°C to 50°C, for example, 40°C to 70°C, for example, 40°C to 50°C, for example, 50°C to 70°C, for example, 60°C to 70°C.

[0022] The second resin domains may have a domain size of at least 50 nm, such as at least 100 nm, such as at least 150 nm, such as at least 200 nm, such as at least 250 nm, such as at least 300 nm, such as at least 350 nm, such as at least 400 nm, such as at least 450 nm, such as at least 500 nm, such as at least 550 nm, such as at least 600 nm, such as at least 650 nm, such as at least 700 nm, such as at least 750 nm, such as at least 800 nm. As used herein, the term "domain size" with respect to resin domains refers to measurements made according to the following procedure: Coated and cured panels are cut to size, embedded in EMBed-812 epoxy resin, and cured at 60°C for 24 hours. Thin sections (<80 nm) are then obtained by sectioning with an ultrathin sectioning microtome and collected on copper TEM grids. Bright-field images are taken with a Tecnai T20 TEM operating at 200 kV. The maximum Feret's diameter of the low-density domains is determined by measuring 10 domains in three different images using ImageJ.

[0023] The electrodeposition coating may optionally further comprise a third glass transition temperature, which, if present, may or may not correspond to the presence of a third resin domain. If present, the third glass transition temperature may be less than -50°C.

[0024] The glass transition temperature may be measured according to the procedure set forth in the Examples section.

[0025] Electrodepositable binder According to the present disclosure, the electrodepositable coating composition further comprises an electrodepositable binder. As used herein, "electrodepositable binder" refers to any suitable inorganic or organic resinous material that may be used in or applied to an electrodepositable coating composition to enable the electrodepositable coating composition to be applied by an electrodeposition process.

[0026] As used herein, the term "electrodepositable coating composition" refers to a composition that can be deposited onto a conductive substrate under the influence of an electrical potential applied between two electrodes immersed in the electrodepositable coating composition, where one of the electrodes is the substrate to be coated.

[0027] The electrodepositable coating composition includes an electrodepositable binder, which may include any suitable electrodepositable binder. For example, the electrodepositable binder may include organic and / or inorganic electrodepositable binders. As used herein, the term "binder" refers to the nonvolatile content of the electrodepositable coating composition, excluding fillers.

[0028] As used herein, an "organic" electrodepositable binder may include a film-forming polymer and / or curing agent that includes a carbon-based material. As used herein, an "inorganic" electrodepositable binder may include a film-forming polymer and / or curing agent that is based on other materials, such as, for example, a silicone-based material. It will be understood that an electrodepositable binder may also include a mixture of organic and inorganic film-forming and / or curing agent materials.

[0029] As used herein, the term "film-forming polymer" is used interchangeably with "polymer" or "resin" and refers to one or more polymers, such as homopolymers and / or copolymers, as well as prepolymers, oligomers, and monomers, that can form a film upon reaction with a curing or crosslinking agent. As used herein, the terms "crosslinker," "crosslinking agent," or "curing agent" refer to a molecule that can form a covalent bond between polymers. For example, a polyisocyanate curing agent may react with active hydrogen groups on a film-forming polymer to result in at least partial curing of the coating composition to form a coating. As used herein, the terms "cure," "curing," or similar terms refer to at least a portion of the coating composition being crosslinked to form a coating.

[0030] The electrodepositable coating composition may include an ionic salt group-containing film-forming polymer, such as a cationic salt group-containing film-forming polymer or an anionic salt group-containing film-forming polymer.

[0031] For example, the ionic salt group-containing film-forming polymer may comprise the reaction product of a reaction mixture comprising: (a) a polyepoxide; (b) a difunctional chain extender; and (c) a monofunctional reactant. Non-limiting examples of such polymers are described in International Application No. PCT / US22 / 73356, paragraphs

[0023] -

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

[0032] As used herein, "cationic salt group-containing film-forming polymer" refers to a polymer containing at least partially neutralized cationic salt groups, such as amine, sulfonium, and / or ammonium salt groups, that impart a positive charge. The cationic salt group-containing film-forming polymer may also contain active hydrogen functional groups. As used herein, the term "active hydrogen functional groups" refers to groups that react with isocyanates, including, for example, hydroxyl groups, primary or secondary amine groups, carbamate, and thiol groups.

[0033] Non-limiting examples of polymers suitable for use as the cationic salt group-containing film-forming polymer of the electrodepositable composition include, but are not limited to, alkyd polymers, acrylics, polyepoxides, polyamides, polyurethanes, polyureas, polyethers, and polyesters, as well as adducts, derivatives, and combinations thereof.

[0034] Cationic salt group-containing film-forming polymers are made cationic and water-dispersible by at least partial neutralization with an acid such as formic acid, acetic acid, methanesulfonic acid, lactic acid, phosphoric acid, and / or sulfamic acid.

[0035] The degree of neutralization of the cationic salt group-containing film-forming polymer may vary depending on the particular polymer involved. However, sufficient acid should be used to sufficiently neutralize the cationic salt group-containing film-forming polymer so that it can be dispersed in an aqueous dispersion medium. For example, the amount of acid used may represent at least 20% of the total theoretical neutralization equivalent. Alternatively, the amount of acid used may exceed 100% of the total theoretical neutralization equivalent. The total amount of acid used to neutralize the cationic salt group-containing film-forming polymer may range between any combination of values, such as 20% or more, to values ​​such as greater than 100%, inclusive. For example, the total amount of acid used to neutralize the active hydrogen-containing, cationic salt group-containing film-forming polymer may be 20%, 35%, 50%, 60%, 80%, or 100% or more, based on the total amines in the cationic salt group-containing film-forming polymer.

[0036] As used herein, the term "anionic salt group-containing film-forming polymer" refers to an anionic polymer containing at least partially neutralized anionic functional groups, such as carboxylic acid and / or phosphate groups, that impart a negative charge. The anionic salt group-containing film-forming polymer may also contain active hydrogen functional groups.

[0037] Non-limiting examples of polymers suitable for use as the anionic salt group-containing film-forming polymer of the electrodepositable binder include, but are not limited to, dry and / or semi-dry and / or saturated alkyd polymers, acrylics, polyepoxides, polyamides, polyurethanes, polyureas, polyethers, polyesters, resinous polyols, phosphate-treated polyepoxides, and phosphate-treated acrylic polymers, alkyd and amine-aldehyde containing vehicles, and adducts, derivatives, and combinations thereof.

[0038] Non-limiting examples of inorganic electrodepositable film-forming polymers include silicone-based film-forming polymers. Non-limiting examples of such polymers are described in International Publication No. WO2021 / 138384A1, paragraphs

[0007] to

[0029] , the cited portions of which are incorporated herein by reference.

[0039] The active hydrogen-containing, ionic salt group-containing film forming polymer has an aromatic content of at least 10 wt%, such as at least 15 wt%, for example at least 20 wt%, such as at least 25 wt%, for example at least 30 wt%, such as at least 35 wt%, for example at least 40 wt%, based on the total weight of the active hydrogen-containing, ionic salt group-containing film forming polymer.

[0040] As used herein, the term "aromatic content" refers to a structure having resonating π bonds where the number of π electrons is 4n+2 (n=1, 2, 3, etc.) according to molecular orbital theory. A non-limiting example of a cyclic aromatic structure is a benzene ring, which has 6 π electrons and n=1. The weight percent aromatic content in a polymer is determined by including only the atoms in the aromatic structure. For example, in the case of a benzene ring, only the six carbon atoms in the ring contribute to the aromatic content of the polymer.

[0041] The ionic salt group-containing film-forming polymer may be present in the electrodepositable coating composition in an amount of at least 40 wt%, such as at least 50 wt%, such as at least 55 wt%, such as at least 60 wt%, based on the total weight of resin solids of the electrodepositable coating composition. The ionic salt group-containing film-forming polymer may be present in the electrodepositable coating composition in an amount of up to 90 wt%, such as up to 80 wt%, such as up to 75 wt%, based on the total weight of resin solids of the electrodepositable coating composition. The ionic salt group-containing film forming polymer may be present in the electrodepositable coating composition in an amount of 40% to 90% by weight, based on the total weight of resin solids of the electrodepositable coating composition, such as 40% to 80% by weight, such as 40% to 75% by weight, for example 50% to 90% by weight, such as 50% to 80% by weight, for example 50% to 75% by weight, such as 55% to 90% by weight, for example 55% to 80% by weight, such as 55% to 75% by weight, for example 60% to 90% by weight, for example 60% to 80% by weight, for example 60% to 75% by weight.

[0042] As used herein, "resin solids" includes the ionic salt group-containing film-forming polymer, the curing agent, and any additional water-dispersible non-pigmentary component(s) present in the electrodepositable coating composition.

[0043] The electrodepositable coating composition of the present disclosure may further comprise a curing agent. The curing agent may react with reactive groups, such as active hydrogen groups, of the ionic salt group-containing film-forming polymer and reactive groups, if present, of the additional resin material to effect curing of the electrodepositable coating composition and form a coating. Non-limiting examples of suitable curing agents include at least partially blocked polyisocyanates and aminoplast resins and / or phenoplast resins, such as phenol-formaldehyde condensates (including their allyl ether derivatives).

[0044] As used herein, "blocked polyisocyanate" refers to a polyisocyanate in which at least a portion of the isocyanato groups are blocked with blocking groups introduced by reacting the free isocyanato groups of the polyisocyanate with a blocking agent. "Blocking" the isocyanato groups means that the isocyanato groups have reacted with the blocking agent, resulting in the blocked isocyanato groups being stable to active hydrogen at ambient temperatures, e.g., room temperature (23°C). The reaction may be reversed under suitable conditions, e.g., at elevated temperatures, e.g., 90°C to 200°C, such that the previously blocked isocyanato groups on the polyisocyanate curing agent are unblocked and available to react with reactive groups, such as active hydrogen groups, on the ionic salt group-containing film-forming polymer, resulting in curing of the coating composition and forming a coating.

[0045] As used herein, "blocking agent" refers to a compound that contains a functional group that is reactive with an isocyanato group, resulting in a blocked isocyanate. As used herein, "blocking group" refers to the residual moiety of the blocking agent that is bonded to an isocyanato group in the blocked polyisocyanate.

[0046] The blocking agent dissociated from the blocked polyisocyanate curing agent during curing may be removed from the coating film by volatilization, or some or all of the blocking agent may remain in the cured coating film.

[0047] Non-limiting examples of blocked polyisocyanate curing agents (including suitable polyisocyanates, blocking components such as blocking groups and / or blocking agents (e.g., but not limited to, 1,2 polyols)) and amounts thereof are described in paragraphs

[0022] to

[0035] of International Publication No. WO2021 / 138583A1, the cited portions of which are incorporated herein by reference.

[0048] Non-limiting examples of blocked polyisocyanates containing blocking groups derived from a blocking agent containing an alpha-hydroxyamide, ester, or thioester, and optionally a second blocking agent, are described in International Publication No. WO 2018 / 148306 A1, paragraphs

[0010] to

[0029] , the cited portions of which are incorporated herein by reference. The blocked polyisocyanate may be a fully blocked polyisocyanate, in which substantially 100% of the isocyanato groups of the polyisocyanate are blocked with one or more blocking groups. Optionally, the blocked polyisocyanate curing agent may be an at least partially blocked polyisocyanate, in which less than 100% of the isocyanato groups are blocked, so long as the coating composition remains a stable dispersion as defined herein.

[0049] The at least partially blocked polyisocyanate may be partially blocked with one or more of the blocking groups described above, with the remaining isocyanato groups remaining reacted with the polymer backbone, for example, as described in U.S. Pat. No. 3,947,338, column 2, line 65 to column 5, line 33, the cited portions of which are incorporated herein by reference.

[0050] The blocked polyisocyanate curing agent may include tris(alkoxycarbonylamino)-1,3,5-triazine (TACT). Non-limiting examples of suitable tris(alkoxycarbonylamino)-1,3,5-triazines include tris(methoxycarbonylamino)-1,3,5-triazine, tris(butoxycarbonylamino)-1,3,5-triazine, and tris(2-ethylhexyloxycarbonylamino)-1,3,5-triazine, and any combination thereof.

[0051] The curing agent may comprise an aminoplast resin or a phenoplast resin. Aminoplast resins are the condensation products of an aldehyde with a substance containing an amino or amide group. Phenoplast resins are formed by the condensation of an aldehyde with a phenol.

[0052] Non-limiting examples of commercially available aminoplast resins include CYMEL 1130 and CYMEL 1156, available under the CYMEL trademark from Allnex Belgium SA / NV, and RESIMENE 750 and RESIMENE 753, available under the RESIMENE trademark from INEOS Melamines. Examples of suitable aminoplast resins and amounts thereof are described in U.S. Pat. No. 3,937,679, column 16, line 3 to column 17, line 47, which is incorporated herein by reference. As disclosed in the aforementioned portion of U.S. Pat. No. 3,937,679, aminoplasts may be used in combination with methylol phenol ethers.

[0053] Suitable aminoplast and phenoplast resins are also described in US Pat. No. 4,812,215, col. 6, line 20 to column 7, line 12, the cited portions of which are incorporated herein by reference.

[0054] Non-limiting examples of further curing agents include silicone-based curing agents. Non-limiting examples of such curing agents are described in paragraphs

[0030] to

[0043] of International Publication No. WO2021 / 138384A1, the cited portions of which are incorporated herein by reference.

[0055] The curing agent may be present in the electrodepositable coating composition in an amount of at least 10% by weight, such as at least 20% by weight, such as at least 25% by weight, based on the total weight of resin solids of the electrodepositable coating composition. The curing agent may be present in the electrodepositable coating composition in an amount of 60% by weight or less, such as 50% by weight or less, such as 45% by weight or less, such as 40% by weight or less, based on the total weight of resin solids of the electrodepositable coating composition. The curing agent may be present in the electrodepositable coating composition in an amount of 10% to 60% by weight, based on the total weight of resin solids of the electrodepositable coating composition, such as 10% to 50% by weight, such as 10% to 45% by weight, such as 10% to 40% by weight, such as 20% to 60% by weight, such as 20% to 50% by weight, such as 20% to 45% by weight, such as 20% to 40% by weight, such as 25% to 60% by weight, such as 25% to 50% by weight, such as 25% to 45% by weight, such as 25% to 40% by weight.

[0056] According to the present disclosure, the electrodepositable coating and / or electrodepositable coating composition optionally further comprises a curing catalyst. As used herein, the term "curing catalyst" is used interchangeably with "catalyst" and refers to a material that catalyzes the curing reaction between components of the electrodepositable coating composition, such as, for example, a curing agent and a film-forming polymer. For example, the catalyst may catalyze a urethane exchange reaction, particularly the deblocking of blocking groups of a blocked polyisocyanate.

[0057] Non-limiting examples of cure catalysts include amine-containing compounds, compounds or complexes of metals (eg, bismuth, cerium, zinc, and / or titanium), and combinations thereof.

[0058] Suitable catalysts for cationic electrodepositable coating compositions include, but are not limited to, metal oxides (e.g., oxides of cerium, zirconium, bismuth) and their salts, zinc compounds or complexes, and / or cyclic guanidines as described in U.S. Pat. No. 7,842,762, column 1, line 53 to column 4, line 18, and column 16, line 62 to column 19, line 8, the cited portions of which are incorporated herein by reference.

[0059] Suitable catalysts for anionic electrodepositable coating compositions include, but are not limited to, latent acid catalysts. Latent acid catalysts are derivatives of acid catalysts that are generally activated by heating. Non-limiting examples of latent acid catalysts are described in paragraph

[0031] of WO2007 / 118024. Further examples of suitable latent acid catalysts include derivatives of acid catalysts such as sulfonic acids, for example, derivatives of paratoluenesulfonic acid, such as pyridinium paratoluenesulfonate.

[0060] The amine-containing curing catalyst may include any suitable amine-containing curing catalyst, such as, but not limited to, curing catalysts including guanidine, imidazole, amidine, and / or derivatives or combinations thereof.

[0061] Non-limiting examples of suitable guanidine curing catalysts are described in International Publication No. WO2018 / 0172519A1, paragraphs

[0039] to

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

[0062] Non-limiting examples of imidazole cure catalysts are described in U.S. Publication No. 2022 / 0154014A1, paragraphs

[0062] to

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

[0063] The amidine cure catalyst may include, by way of non-limiting example, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0064] The zinc-containing catalyst may include, but is not limited to, zinc metal salts and / or complexes such as zinc(II) amidine complex, zinc octoate, zinc naphthenate, zinc tartarate, zinc carboxylate having 8 to 14 carbon atoms in the carboxyl group, zinc acetate, zinc sulfonate, zinc methanesulfonate, or any combination thereof. The zinc(II) amidine complex may contain amidine and carboxylate ligands.

[0065] The curing catalyst may be present in the electrodepositable coating composition in any suitable amount. For example, the amine and / or zinc-containing curing catalyst may be present in the coating composition in an amount of at least 0.1 wt.%, such as at least 0.2 wt.%, for example at least 0.5 wt.%, for example at least 0.8 wt.%, for example at least 1 wt.%, for example at least 1.5 wt.%, based on the total weight of resin solids of the coating composition. The amine and / or zinc-containing curing catalyst may be present in the coating composition in an amount of 7 wt.% or less, such as 4 wt.% or less, for example 2 wt.% or less, for example 1.5 wt.% or less, for example 1 wt.% or less, based on the total weight of resin solids of the coating composition. The amine and / or zinc containing curing catalyst may be present in the coating composition in an amount of 0.1wt% to 7wt%, based on the total weight of resin solids of the coating composition, such as 0.1wt% to 4wt%, for example 0.1wt% to 2wt%, such as 0.1wt% to 1.5wt%, for example 0.1wt% to 1wt%, such as 0.2wt% to 7wt%, for example 0.2wt% to 4wt%, such as 0.2wt% to 2wt%, for example 0.2wt% to 1.5wt%, for example 0.2wt% to 1wt%, such as 0.5wt% to 7wt%, for example 0.5wt% to 4wt%. , for example 0.5% to 2% by weight, such as 0.5% to 1.5% by weight, for example 0.5% to 1% by weight, such as 0.8% to 7% by weight, for example 0.8% to 4% by weight, for example 0.8% to 2% by weight, such as 0.8% to 1.5% by weight, for example 0.8% to 1% by weight, such as 1% to 7% by weight, for example 1% to 4% by weight, for example 1% to 2% by weight, such as 1% to 1.5% by weight, for example 1.5% to 7% by weight, for example 1.5% to 4% by weight, for example 1.5% to 2% by weight.

[0066] The curing catalyst may include a bismuth catalyst. Non-limiting examples of bismuth curing catalysts and amounts thereof are described in International Publication No. WO2021 / 138583A1, paragraphs

[0036] to

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

[0067] The curing catalyst is, for example, Ti(OR 1 ) 4, where R 1 is alkyl or aryl, e.g., R 1 is C3-C20 alkyl, for example, R 1 is n-butyl, for example, tetrabutyl titanate.

[0068] An electrodepositable coating composition may be nearly free, substantially free, or completely free of catalytic tin. An electrodepositable coating composition may be nearly free, substantially free, or completely free of catalytic tin. As used herein, an electrodepositable coating composition is "nearly free" of catalytic tin if the catalytic tin is present in an amount of less than 0.1 wt. %, based on the total weight of the electrodepositable coating composition. As used herein, an electrodepositable coating composition is "substantially free" of catalytic tin if the catalytic tin is present in an amount of less than 0.01%, based on the total weight of the electrodepositable coating composition. As used herein, an electrodepositable coating composition is "completely free" of catalytic tin if the catalytic tin is present in an amount of 0.001%, based on the total weight of the electrodepositable coating composition.

[0069] Organic resin component According to the present disclosure, the electrodeposition coating and / or electrodepositable coating composition may further comprise at least one organic resin component different from the main component of the electrodepositable binder, such as, for example, an active hydrogen-containing, ionic salt group-containing film-forming polymer and a curing agent.

[0070] As used herein, "organic resin component" refers to an organic-based polymer component.

[0071] The organic resin component may have a weight average molecular weight of at least 1,000 g / mol or more.

[0072] The organic resin component may be present in an amount of at least 0.01 wt.%, such as at least 0.1 wt.%, such as at least 0.3 wt.%, such as at least 0.5 wt.%, such as at least 0.75 wt.%, such as at least 1 wt.%, such as at least 3 wt.%, such as at least 5 wt.%, such as at least 10 wt.%, such as at least 15 wt.%, such as at least 20 wt.%, such as at least 25 wt.%, based on the total weight of the electrodepositable coating and / or the electrodepositable binder. The organic resin component may be present in an amount of 50 wt% or less, such as 35 wt% or less, such as 30 wt% or less, such as 25 wt% or less, such as 20 wt% or less, such as 15 wt% or less, such as 10 wt% or less, such as 5 wt% or less, such as 3 wt% or less, such as 2 wt% or less, such as 1.5 wt% or less, such as 1 wt% or less, such as 0.75 wt% or less, based on the total weight of the electrodeposition coating and / or electrodepositable binder. The organic resin component may be present in an amount of 0.01wt% to 50wt%, based on the total weight of the electrodepositable coating and / or electrodepositable binder, such as 0.01wt% to 35wt%, for example 0.01wt% to 30wt%, such as 0.01wt% to 25wt%, for example 0.01wt% to 20wt%, such as 0.01wt% to 15wt%, for example 0.01wt% to 10wt%, such as 0.01wt% to 5wt%, for example 0.01wt% to 3wt%, such as 0.01wt% to 2wt%, for example 0.01wt% to 1.5wt%, for example 0.01wt% to 1wt%, such as 0.01wt% ~0.75% by weight, for example 0.1% by weight to 50% by weight, for example 0.1% by weight to 35% by weight, for example 0.1% by weight to 30% by weight, for example 0.1% by weight to 25% by weight, for example 0.1% by weight to 20% by weight, for example 0.1% by weight to 15% by weight, for example 0.1% by weight to 10% by weight, for example 0.1% by weight to 5% by weight, for example 0.1% by weight to 3% by weight, for example 0.1% by weight to 2% by weight, for example 0.1% by weight to 1.5% by weight, for example 0.1% by weight to 1% by weight, for example 0.1% by weight to 0.75% by weight, for example 0.3% by weight to 35% by weight, for example 0.3% by weight to 30% by weight, for example 0.3% by weight to 25% by weight, for example 0.3% by weight to 20% by weight, for example 0.3% by weight to 15% by weight, for example 0.3% by weight to 10% by weight, for example 0.3% by weight to 5% by weight, for example 0.3% by weight to 3% by weight, for example 0.3% by weight to 2% by weight, for example 0.3% by weight to 1.5% by weight, for example 0.3% by weight to 1% by weight, for example 0.3% by weight to 0.75% by weight, for example 0.5% by weight to 50% by weight, for example 0.5% by weight to 35% by weight, for example 0.5% by weight to 30% by weight, for example 0.5% by weight to 25% by weight, for example 0.5% by weight to 20% by weight, for example 0.5% by weight to 15% by weight, for example 0 0.5% to 10% by weight, for example 0.5% to 5% by weight, for example 0.5% to 3% by weight, for example 0.5% to 2% by weight, for example 0.5% to 1.5% by weight, for example 0.5% to 1% by weight, for example 0.5% to 0.75% by weight, for example 1% to 50% by weight, for example 1% to 35% by weight, for example 1% to 30% by weight, for example 1% to 25% by weight, for example 1% to 20% by weight, for example 1% to 15% by weight, for example 1% to 10% by weight, for example 1% to 5% by weight, for example 1% to 3% by weight, for example 1% to 2% by weight, for example 1% to 1.5% by weight, for example 3% to 50% by weight, for example 3% to 35% by weight, for example 3% to 30% by weight, for example 3% to 25% by weight, for example 3% to 20% by weight, for example 3% to 15% by weight, for example 3% to 10% by weight, for example 3% to 5% by weight, for example 5% to 50% by weight, for example 5% to 35% by weight, for example 5% to 30% by weight, for example 5% to 25% by weight, for example 5% to 20% by weight, for example 5% to 15% by weight, for example 5% to 10% by weight, for example 10% to 50% by weight, for example 10% to 35% by weight, for example It may be present in an amount of, for example, 10% to 30% by weight, such as 10% to 25% by weight, for example 10% to 20% by weight, for example 10% to 15% by weight, such as 15% to 50% by weight, for example 15% to 35% by weight, for example 15% to 30% by weight, such as 15% to 25% by weight, for example 15% to 20% by weight, such as 20% to 50% by weight, for example 20% to 35% by weight, for example 20% to 30% by weight, such as 20% to 25% by weight, for example 25% to 50% by weight, for example 25% to 35% by weight, for example 25% to 30% by weight.

[0073] Non-limiting examples of suitable organic resin components include: (1) an addition polymer comprising the polymerization product of a polymerizable dispersant and a second stage ethylenically unsaturated monomer composition comprising second stage hydroxyl-functional (meth)acrylamide monomers and / or second stage hydroxyl-functional (meth)acrylate monomers; (2) a hydroxyl-functional addition polymer comprising constitutional units, at least 70% of which comprise Formula VIII: -[-C(R 1 )2-C(R 1 )(OH)-]- (VIII), In the formula, R 1are each independently 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 % are based on all the building blocks of the hydroxyl-functional addition polymer, including (3) a cellulose derivative, (4) a polyvinylformamide, (5) a cationic epoxy microgel, (6) a polyamine-dialdehyde adduct, (7) a polyetheramine adduct, or a combination thereof.

[0074] As used herein, the term "addition polymer" refers to a polymerization product that comprises, at least in part, the residues of unsaturated monomers.

[0075] Addition polymer comprising the polymerization product of a polymerizable dispersant and a second stage ethylenically unsaturated monomer composition comprising second stage hydroxyl-functional (meth)acrylamide monomers and / or second stage hydroxyl-functional (meth)acrylate monomers. The organic resin component may comprise an addition polymer comprising the polymerization product of a polymerizable dispersant and a second stage ethylenically unsaturated monomer composition comprising second stage hydroxyl-functional (meth)acrylamide monomers and / or second stage hydroxyl-functional (meth)acrylate monomers.

[0076] In accordance with the present disclosure, the electrodeposition coating and / or electrodepositable coating composition may include an addition polymer.

[0077] The addition polymer may include an acrylic polymer comprising the polymerization product of a polymerizable dispersant and an aqueous dispersion of a second-stage ethylenically unsaturated monomer composition. As used herein, the term "acrylic polymer" refers to a polymerization product comprising, at least in part, residues of a (meth)acrylic monomer. The polymerization product may be formed by a two-stage polymerization process, in which a polymerizable dispersant is polymerized in a first stage, and a second-stage ethylenically unsaturated monomer composition is added to the aqueous dispersion of the polymerizable dispersant and polymerized in the presence of the polymerizable dispersant participating in the polymerization to form the acrylic polymer in a second stage. Non-limiting examples of acrylic polymers comprising the polymerization product of a polymerizable dispersant and an aqueous dispersion of a second-stage ethylenically unsaturated monomer composition are described in International Publication No. WO 2018 / 160799 A1, paragraphs

[0013] to

[0055] , the citations of which are incorporated herein by reference.

[0078] The addition polymer may alternatively comprise the polymerization product of a polymerizable dispersant and a second stage ethylenically unsaturated monomer composition that includes second stage (meth)acrylamide monomers.

[0079] According to the present disclosure, polymeric dispersants may include polymeric dispersants having sufficient salt group content to stably disperse and participate in the subsequent polymerization of the second-stage ethylenically unsaturated monomer composition to provide an addition polymer that is stable in the electrodepositable coating composition. Although reference is made to first-stage polymerized polymeric dispersants, it will be understood that preformed or commercially available dispersants may also be used, and that preformation of the polymeric dispersant is considered the first-stage polymerization.

[0080] According to the present disclosure, the first stage polymerized polymerizable dispersant may comprise the polymerization product of a first stage ethylenically unsaturated monomer composition.

[0081] The first-stage ethylenically unsaturated monomer composition includes one or more monomers that allow for the incorporation of ionic salt groups into the polymerizable dispersant, such that the polymerizable dispersant comprises an ionic salt group-containing polymerizable dispersant. For example, the polymerizable dispersant may include cationic salt groups, such that the polymerizable dispersant comprises a cationic salt group-containing polymerizable dispersant, or may include anionic salt groups, such that the polymerizable dispersant comprises an anionic salt group-containing polymerizable dispersant. The cationic salt groups may be formed by the incorporation of an epoxide-functional unsaturated monomer, an amino-functional unsaturated monomer, or a combination thereof, followed by neutralization. For example, the polymerizable dispersant may comprise a cationic salt group-containing polymerizable dispersant comprising the polymerization product of a first-stage ethylenically unsaturated monomer that includes an epoxide-functional ethylenically unsaturated monomer and / or an amino-functional ethylenically unsaturated monomer. The anionic salt groups may be formed by the incorporation of an acid-functional unsaturated monomer, followed by neutralization. For example, the polymeric dispersant may comprise an anionic salt group-containing polymeric dispersant comprising the polymerization product of a first stage ethylenically unsaturated monomer composition comprising an acid-functional ethylenically unsaturated monomer.

[0082] The first-stage ethylenically unsaturated monomer composition may optionally contain an epoxide-functional monomer. The epoxide-functional monomer allows for the incorporation of epoxide functionality into the polymerizable dispersant. The epoxide functionality can be converted to a cationic salt group via reaction of the epoxide functionality with an amine and neutralization with an acid. 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, such as 5% to 40% by weight, such as 5% to 30% by weight, for example 5% to 25% by weight, such as 5% to 20% by weight, for example 10% to 50% by weight, such as 10% to 40% by weight, for example 10% to 30% by weight, such as 10% to 25% by weight, for example 10% to 20% by weight, such as 20% to 50% by weight, for example 20% to 40% by weight, for example 20% to 30% by weight, for example 20% to 25% by weight, based on the total weight of the first stage ethylenically unsaturated monomer composition.

[0083] The first-stage ethylenically unsaturated monomer composition may optionally include an amino-functional monomer. The amino-functional monomer allows for the incorporation of amino-functional groups into the polymerizable dispersant. The amino-functional groups can be converted to cationic salt groups by neutralization with an acid. The amino-functional monomer may include any suitable amino-functional unsaturated monomer, such as N-alkylaminoalkyl(meth)acrylates, N,N-(dialkyl)aminoalkyl(meth)acrylates, aminoalkyl(meth)acrylates, and the like. 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, and combinations thereof. The amino functional monomer may be present in an amount of 5% to 50% by weight, such as 5% to 40% by weight, such as 5% to 30% by weight, for example 5% to 25% by weight, such as 5% to 20% by weight, for example 10% to 50% by weight, such as 10% to 40% by weight, for example 10% to 30% by weight, such as 10% to 25% by weight, for example 10% to 20% by weight, such as 20% to 50% by weight, for example 20% to 40% by weight, for example 20% to 30% by weight, for example 20% to 25% by weight, based on the total weight of the first stage ethylenically unsaturated monomer composition.

[0084] The first stage ethylenically unsaturated monomer composition may optionally include an acid-functional ethylenically unsaturated monomer, which allows for the incorporation of anionic salt groups into the polymerizable dispersant upon neutralization with a base. The acid-functional ethylenically unsaturated monomer may include a phosphoric acid or carboxylic acid functional ethylenically unsaturated monomer, such as (meth)acrylic acid. The acid functional monomer may be present in the first stage ethylenically unsaturated monomer composition in an amount of 5% to 50% by weight, based on the total weight of the first stage ethylenically unsaturated monomer composition, such as 5% to 40% by weight, such as 5% to 30% by weight, for example 5% to 25% by weight, such as 5% to 20% by weight, for example 10% to 50% by weight, such as 10% to 40% by weight, for example 10% to 30% by weight, such as 10% to 25% by weight, for example 10% to 20% by weight, such as 20% to 50% by weight, for example 20% to 40% by weight, such as 20% to 30% by weight, for example 20% to 25% by weight.

[0085] The first stage ethylenically unsaturated monomer composition is C1-C 18 It may optionally further comprise at least one of an alkyl (meth)acrylate, a first-stage hydroxyl-functional (meth)acrylate, a vinyl aromatic compound, and / or a monomer containing two or more ethylenically unsaturated groups per molecule.

[0086] The first stage ethylenically unsaturated monomer composition is C1-C 18 Optionally, it may further comprise a monoolefinic aliphatic compound such as an alkyl (meth)acrylate. 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, and the like.18 The alkyl (meth)acrylate may be present in the first stage ethylenically unsaturated monomer composition in an amount of 30% to 90% by weight, based on the total weight of the first stage ethylenically unsaturated monomer composition, such as 30% to 80% by weight, such as 30% to 70% by weight, for example 30% to 60% by weight, such as 40% to 90% by weight, for example 40% to 80% by weight, for example 40% to 70% by weight, such as 40% to 60% by weight, for example 50% to 90% by weight, such as 50% to 80% by weight, for example 50% to 70% by weight, such as 50% to 60% by weight, for example 60% to 90% by weight, such as 60% to 80% by weight, for example 60% to 70% by weight, for example 70% to 90% by weight, for example 70% to 80% by weight. As used herein, terms such as "(meth)acrylate" encompass both acrylates and methacrylates.

[0087] The ethylenically unsaturated monomer composition may optionally include a hydroxyl-functional (meth)acrylate. As used herein, the term "hydroxyl-functional (meth)acrylate" refers collectively to both acrylates and methacrylates having hydroxyl functionality, i.e., containing at least one hydroxyl functional group in the molecule. Hydroxyl-functional (meth)acrylates may include, for example, hydroxyalkyl (meth)acrylates such as hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, and combinations thereof. The hydroxyl functional (meth)acrylate may be present in the first stage ethylenically unsaturated monomer composition in an amount of from 1 wt% to 40 wt%, based on the total weight of the first stage ethylenically unsaturated monomer composition, such as from 1 wt% to 30 wt%, such as from 1 wt% to 25 wt%, for example from 1 wt% to 15 wt%, such as from 5 wt% to 40 wt%, for example from 5 wt% to 30 wt%, such as from 5 wt% to 25 wt%, for example from 5 wt% to 15 wt%, such as from 10 wt% to 40 wt%, for example from 10 wt% to 30 wt%, such as from 10 wt% to 25 wt%, for example from 10 wt% to 15 wt%.

[0088] The first stage ethylenically unsaturated monomer composition may comprise a vinyl aromatic compound. Non-limiting examples of suitable vinyl aromatic compounds include styrene, alpha-methylstyrene, alpha-chloromethylstyrene, and / or vinyltoluene. The vinyl aromatic compound may be present in the first stage ethylenically unsaturated monomer composition in an amount of 0.5% to 40% by weight, based on the total weight of the first stage ethylenically unsaturated monomer composition, such as 0.5% to 30% by weight, such as 0.5% to 20% by weight, for example 0.5% to 15% by weight, such as 0.5% to 10% by weight, for example 1% to 40% by weight, such as 1% to 30% by weight, for example 1% to 20% by weight, such as 1% to 15% by weight, for example 1% to 10% by weight, such as 5% to 40% by weight, for example 5% to 30% by weight, such as 5% to 20% by weight, for example 5% to 15% by weight, such as 5% to 10% by weight, for example 10% to 40% by weight, such as 10% to 30% by weight, for example 10% to 20% by weight, for example 10% to 15% by weight.

[0089] The first-stage ethylenically unsaturated monomer composition may optionally include a monomer containing two or more ethylenically unsaturated groups per molecule. The monomer containing two or more ethylenically unsaturated groups per molecule may include a monomer having two ethylenically unsaturated groups per molecule. Examples of suitable monomers having two ethylenically unsaturated groups per molecule include ethylene glycol dimethacrylate, allyl methacrylate, hexanediol diacrylate, methacrylic anhydride, tetraethylene glycol diacrylate, and / or tripropylene glycol diacrylate. Examples of monomers having three or more ethylenically unsaturated groups per molecule include ethoxylated trimethylolpropane triacrylate having 0-20 ethoxy units, [ethoxylated] trimethylolpropane trimethacrylate having 0-20 ethoxy units, dipentaerythritol triacrylate, pentaerythritol tetraacrylate, and / or dipentaerythritol pentaacrylate. The monomer containing two or more ethylenically unsaturated groups per molecule may be present in the first stage ethylenically unsaturated monomer composition in an amount of 0.1 wt% to 10 wt%, based on the total weight of the first stage ethylenically unsaturated monomer composition, such as 0.1 wt% to 5 wt%, for example 0.1 wt% to 3 wt%, for example 1 wt% to 10 wt%, for example 1 wt% to 5 wt%, for example 1 wt% to 3 wt%, for example 3 wt% to 10 wt%, for example 3 wt% to 5 wt%, for example 5 wt% to 10 wt%. The use of a monomer containing two or more ethylenically unsaturated groups per molecule in the first stage ethylenically unsaturated monomer composition can result in a polymeric dispersant containing ethylenically unsaturated groups. Thus, the polymeric dispersant may contain ethylenically unsaturated groups.

[0090] The first-stage ethylenically unsaturated monomer composition may include a first-stage (meth)acrylamide monomer. As used herein, the term "first stage" with respect to a monomer, such as a (meth)acrylamide monomer, is intended to refer to the monomer used during polymerization of the polymerizable dispersant, and the resulting polymerizable dispersant includes residues thereof. As used herein, terms such as "(meth)acrylamide" encompass both acrylamide and methacrylamide. The first-stage (meth)acrylamide monomer may include any suitable (meth)acrylamide monomer, such as, for example, (meth)acrylamide, a substituted or unsubstituted monoalkyl (meth)acrylamide monomer, or a substituted or unsubstituted dialkyl (meth)acrylamide monomer. Non-limiting examples of first-stage (meth)acrylamide monomers include (meth)acrylamide, C1-C 18 Examples include alkyl(meth)acrylamide monomers, hydroxyl-functional (meth)acrylamide monomers, and the like.

[0091] The first stage (meth)acrylamide monomer of the first stage ethylenically unsaturated monomer composition is C1-C 18 Alkyl (meth)acrylamide monomers may optionally be included. 18 Examples 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, and t-butyl(meth)acrylamide. 18The alkyl(meth)acrylamide monomer may be present in the first stage ethylenically unsaturated monomer composition in an amount of 30% to 90% by weight, based on the total weight of the first stage ethylenically unsaturated monomer composition, such as 30% to 80% by weight, such as 30% to 70% by weight, for example 30% to 60% by weight, such as 40% to 90% by weight, for example 40% to 80% by weight, for example 40% to 70% by weight, such as 40% to 60% by weight, for example 50% to 90% by weight, such as 50% to 80% by weight, for example 50% to 70% by weight, such as 50% to 60% by weight, for example 60% to 90% by weight, such as 60% to 80% by weight, for example 60% to 70% by weight, for example 70% to 90% by weight, for example 70% to 80% by weight.

[0092] The ethylenically unsaturated monomer composition may optionally include a first-stage hydroxyl-functional (meth)acrylamide monomer. As used herein, the term "hydroxyl-functional (meth)acrylamide" refers collectively to both acrylamides and methacrylamides that have hydroxyl functionality, i.e., contain at least one hydroxyl functional group in the molecule. The first-stage hydroxyl-functional (meth)acrylamide monomer may include, 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, and combinations thereof. The first stage hydroxyl functional (meth)acrylamide monomer may be present in the first stage ethylenically unsaturated monomer composition in an amount of from 1 wt% to 40 wt%, based on the total weight of the first stage ethylenically unsaturated monomer composition, such as from 1 wt% to 30 wt%, such as from 1 wt% to 25 wt%, for example from 1 wt% to 15 wt%, such as from 5 wt% to 40 wt%, for example from 5 wt% to 30 wt%, such as from 5 wt% to 25 wt%, for example from 5 wt% to 15 wt%, such as from 10 wt% to 40 wt%, for example from 10 wt% to 30 wt%, such as from 10 wt% to 25 wt%, for example from 10 wt% to 15 wt%.

[0093] Polymerizable dispersants can be prepared in organic solution by techniques well known in the art. For example, they can be prepared by conventional free-radical initiated solution polymerization techniques in which the first-stage ethylenically unsaturated monomer composition is dissolved in a solvent or mixture of solvents and polymerized in the presence of a free-radical initiator. Examples of suitable solvents that can be used in organic solution polymerization include alcohols such as ethanol, tert-butanol, and tert-amyl alcohol; ketones such as acetone and methyl ethyl ketone; and ethers such as the dimethyl ether of ethylene glycol. Examples of suitable free-radical initiators include those that are soluble in the monomer mixture, such as azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), azobis(alpha, gamma-dimethylvaleronitrile), tert-butyl perbenzoate, tert-butyl peracetate, benzoyl peroxide, and di-tert-butyl peroxide. The free radical initiator may be present in an amount of 0.01% to 6% by weight, such as 1.0% to 4.0% by weight, such as 2.0% to 3.5% by weight, based on the total weight of the first stage ethylenically unsaturated monomer composition. In an example, the solvent may first be heated to reflux, and a mixture of the first stage ethylenically unsaturated monomer composition and the free radical initiator may be slowly added to the refluxing solvent. The reaction mixture may be held at the polymerization temperature to reduce the free monomer content to less than 1.0% by weight, such as less than 0.5% by weight, based on the total weight of the first stage ethylenically unsaturated monomer composition.

[0094] The synthesis of polymeric dispersants may involve the use of chain transfer agents, such as those soluble in the mixture of monomers. Suitable non-limiting examples of such agents include alkyl mercaptans (e.g., tert-dodecyl mercaptan), ketones (e.g., methyl ethyl ketone), and chlorohydrocarbons (e.g., chloroform).

[0095] The polymeric dispersant has a z-average molecular weight (M z) may be 200,000 g / mol to 2,000,000 g / mol, for example, 200,000 g / mol to 1,200,000 g / mol, for example, 200,000 g / mol to 900,000 g / mol, for example, 250,000 g / mol to 2,000,000 g / mol, for example, 250,000 g / mol to 1,200,000 g / mol, for example, 250,000 g / mol to 900,000 g / mol, for example, 300,000 to 2,000,000 g / mol, for example, 300,000 g / mol to 1,200,000 g / mol, for example, 300,000 g / mol to 900,000 g / mol.

[0096] According to the present disclosure, the polymeric dispersant may have a weight average molecular weight of 150,000 g / mol to 750,000 g / mol, such as 150,000 g / mol to 400,000 g / mol, for example 150,000 g / mol to 300,000 g / mol, for example 175,000 g / mol to 750,000 g / mol, such as 175,000 g / mol to 400,000 g / mol, for example 175,000 g / mol to 300,000 g / mol, such as 200,000 g / mol to 750,000 g / mol, for example 200,000 g / mol to 400,000 g / mol, for example 200,000 g / mol to 300,000 g / mol.

[0097] The ionic groups in the polymeric dispersant may be formed by at least partially neutralizing basic or acidic groups present in the polymeric dispersant with an acid or base, respectively. The ionic groups in the polymer molecule may be charge-neutralized with a counterion. The ionic group and the charge-neutralizing counterion may together form a salt group, and the polymeric dispersant includes a polymeric dispersant containing an ionic salt group.

[0098] Thus, the polymeric dispersant may be at least partially neutralized, for example, by treatment with an acid, to form a water-dispersible cationic salt group-containing polymeric dispersant before or during dispersion in a dispersing medium containing water. As used herein, the term "cationic salt group-containing polymeric dispersant" refers to a cationic polymeric dispersant containing at least partially neutralized cationic functional groups, such as sulfonium and ammonium groups, that impart a positive charge. The polymeric dispersant may be neutralized to a degree 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, such as amino groups, theoretically present in the polymer. As mentioned above, amines may be incorporated into the cationic polymeric dispersant by reaction of epoxide functional groups present in the polymeric dispersant with the amine. The dispersing step may be accomplished by combining a neutralized or partially neutralized cationic salt group-containing polymeric dispersant with a dispersed phase dispersing medium. Neutralization and dispersion may also be accomplished in one step by combining the polymeric dispersant with 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 in the range of 5 to 9.

[0099] The cationic salt group-containing polymerizable dispersant may contain sufficient cationic salt group content to stabilize the subsequent polymerization of the second stage ethylenically unsaturated monomer composition (described below) and provide an addition polymer that is stable in the cationic electrodepositable coating composition. The cationic salt group-containing polymerizable dispersant may also have sufficient cationic salt group content so that, when used with other film-forming resins in a cationic electrodepositable coating composition, the composition, upon being subjected to electrodeposition conditions, deposits as a coating on the substrate. The cationic salt group-containing polymerizable dispersant may, for example, contain 0.1 to 5.0 milliequivalents, e.g., 0.3 to 1.1 milliequivalents, of cationic base per gram of cationic salt group-containing polymerizable dispersant.

[0100] According to the present disclosure, polymeric dispersants may be at least partially neutralized, for example, by treatment with a base, before or during dispersion in a dispersion medium containing water, to form a water-dispersible anionic salt group-containing polymeric dispersant. As used herein, the term "anionic salt group-containing polymeric dispersant" refers to an anionic polymeric dispersant containing at least partially neutralized anionic functional groups, such as carboxylic acid groups and phosphate groups, that impart a negative charge. Non-limiting examples of suitable bases include amines, such as tertiary amines. The polymeric dispersant may be neutralized to at least 50% of its total theoretical neutralization equivalent, in some cases at least 70%, and in other cases 100% or more. The dispersion step may be achieved by combining the neutralized or partially neutralized anionic salt group-containing polymeric dispersant with the dispersion medium of the dispersed phase. Neutralization and dispersion may be achieved in one step by combining the polymeric dispersant with the dispersion medium. The polymerizable dispersant (or a salt thereof) may be added to the dispersion medium, or the dispersion medium may be added to the polymerizable dispersant (or a salt thereof). The pH of the dispersion may be within the range of 5 to 9.

[0101] The anionic salt group-containing polymerizable dispersant may contain sufficient anionic salt group content to stabilize the subsequent polymerization of the second stage ethylenically unsaturated monomer composition (described below) and provide an addition polymer that is stable in the anionic electrodepositable coating composition. The anionic salt group-containing polymerizable dispersant may also have sufficient anionic salt group content so that, when used with other film-forming resins in an anionic electrodepositable coating composition, the composition, upon being subjected to electrodeposition conditions, deposits as a coating on the substrate. The anionic salt group-containing polymerizable dispersant may contain 0.1 to 5.0 milliequivalents, e.g., 0.3 to 1.1 milliequivalents, of anionic base per gram of anionic salt group-containing polymerizable dispersant.

[0102] According to the present disclosure, the second stage ethylenically unsaturated monomer composition comprises a monomer containing 3 or more ethylenically unsaturated groups per molecule and a C1-C 18and at least one other monomer including an alkyl (meth)acrylate, a hydroxyl-functional (meth)acrylate, a vinyl aromatic compound, or any combination thereof. The second-stage ethylenically unsaturated monomer composition may be substantially free, or in some cases completely free, of diene monomer. As used herein, when a second-stage ethylenically unsaturated monomer composition is described as being "substantially free" of diene monomer, it means that diene monomer, if present, is present in the monomer composition in an amount less than 10% by weight, e.g., less than 5% by weight, less than 2% by weight, in some cases less than 1% by weight, or less than 0.1% by weight, based on the total weight of the second-stage ethylenically unsaturated monomer composition.

[0103] Non-limiting examples of monomers containing three or more ethylenically unsaturated groups per molecule include, for example, trimethylolpropane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, ethoxylated trimethylolpropane triacrylate having 0 to 20 ethoxy units, and ethoxylated trimethylolpropane trimethacrylate having 0 to 20 ethoxy units. The ethylenically unsaturated monomer(s) having three or more sites of unsaturation are used in an amount of 0.1 to 10% by weight, for example, 0.1 to 5% by weight, based on the total weight of the second stage ethylenically unsaturated monomer composition.

[0104] The second stage ethylenically unsaturated monomer composition comprises, based on the total weight of the second stage ethylenically unsaturated monomer composition, C1-C 18 If alkyl (meth)acrylate is contained, it may be contained in an amount of 20 to 80% by weight, for example, 20 to 60% by weight.

[0105] The second stage ethylenically unsaturated monomer composition may include, if present at all, 5 to 20 wt. % of the hydroxyl-functional (meth)acrylate, such as 5 to 15 wt. %, based on the total weight of the second stage ethylenically unsaturated monomer composition.

[0106] The second stage ethylenically unsaturated monomer composition may contain the vinyl aromatic compound, if present at all, in an amount of 20 to 80 wt %, such as 20 to 60 wt %, based on the total weight of the second stage ethylenically unsaturated monomer composition.

[0107] According to the present disclosure, the second-stage ethylenically unsaturated monomer composition comprises, consists essentially of, or consists solely of one or more second-stage (meth)acrylamide monomers. As used herein, the term "second stage" with respect to a monomer, such as a (meth)acrylamide monomer, is intended to refer to the monomer used in the second polymerization step of the addition polymer that is polymerized in the presence of a preformed polymerizable dispersant, and the resulting addition polymer includes the residue thereof. The (meth)acrylamide monomer may include any suitable (meth)acrylamide monomer, such as, for example, (meth)acrylamide, substituted or unsubstituted monoalkyl (meth)acrylamide, or substituted or unsubstituted dialkyl (meth)acrylamide. Non-limiting examples include (meth)acrylamide, C1-C 18 Examples include alkyl (meth)acrylamides, hydroxyl-functional (meth)acrylamides, and the like.

[0108] The second stage ethylenically unsaturated monomer composition may comprise, consist essentially of, or consist solely of a (meth)acrylamide, such as (meth)acrylamide or acrylamide. The (meth)acrylamide monomer may be present in the second stage ethylenically unsaturated monomer composition in an amount of 20% to 100% by weight, based on the total weight of the second stage ethylenically unsaturated monomer composition, such as 20% to 99% by weight, such as 20% to 90% by weight, such as 20% to 80% by weight, such as 20% to 70% by weight, such as 20% to 60% by weight, such as 20% to 50% by weight, such as 30% to 100% by weight, for example. For example, 30% by weight to 99% by weight, for example, 30% by weight to 90% by weight, for example, 30% by weight to 80% by weight, for example, 30% by weight to 70% by weight, for example, 30% by weight to 60% by weight, for example, 30% by weight to 50% by weight, for example, 40% by weight to 100% by weight, for example, 40% by weight to 99% by weight, for example, 40% by weight to 90% by weight, for example, 40% by weight to 80% by weight, for example, 40% by weight to 70% by weight, for example, 40% by weight to 60% by weight, for example, 40% by weight to 5 0% by weight, for example 50% to 100% by weight, for example 50% to 99% by weight, for example 50% to 90% by weight, for example 50% to 80% by weight, for example 50% to 70% by weight, for example 50% to 60% by weight, for example 60% to 100% by weight, for example 60% to 99% by weight, for example 60% to 90% by weight, for example 60% to 80% by weight, for example 60% to 70% by weight, for example 70% to 100% by weight, e.g. It may be present in an amount of, for example, 70% to 99% by weight, such as 70% to 90% by weight, for example 70% to 80% by weight, for example 80% to 100% by weight, such as 80% to 99% by weight, for example 80% to 90% by weight, for example 90% to 100% by weight, such as 90% to 99% by weight, for example 95% to 100% by weight, such as 95% to 99% by weight, for example 95% to 100% by weight, such as 95% to 99% by weight.

[0109] The second-stage ethylenically unsaturated monomer composition may comprise, consist essentially of, or consist solely of a second-stage hydroxyl-functional (meth)acrylamide monomer. The second-stage hydroxyl-functional (meth)acrylamide monomer may comprise a primary hydroxyl group. The second-stage hydroxyl-functional (meth)acrylamide monomer may comprise a secondary hydroxyl group. The second-stage hydroxyl-functional (meth)acrylamide monomer may comprise one or more C1-C9 hydroxyalkyl (meth)acrylamides, such as C1-C6 hydroxyalkyl (meth)acrylamides, and further, such as C1-C5 hydroxyalkyl (meth)acrylamides, including hydroxymethyl (meth)acrylamide, hydroxyethyl (meth)acrylamide, hydroxypropyl (meth)acrylamide, 2-hydroxypropyl (meth)acrylamide, hydroxybutyl (meth)acrylamide, hydroxypentyl (meth)acrylamide, or any combination thereof.

[0110] The second stage hydroxyl functional (meth)acrylamide monomer may be present in the second stage ethylenically unsaturated monomer composition in an amount of 20% to 100% by weight, based on the total weight of the second stage ethylenically unsaturated monomer composition, such as 20% to 99% by weight, for example 20% to 90% by weight, such as 20% to 80% by weight, for example 20% to 70% by weight, for example 20% to 60% by weight, such as 20% to 50% by weight, for example 30% by weight to 100% by weight, for example 30% to 99% by weight, for example 30% to 90% by weight, for example 30% to 80% by weight, for example 30% to 70% by weight, for example 30% to 60% by weight, for example 30% to 50% by weight, for example 40% to 100% by weight, for example 40% to 99% by weight, for example 40% to 90% by weight, for example 40% to 80% by weight, for example 40% to 70% by weight, for example 40% to 60% by weight, 40% by weight to 50% by weight, for example 50% by weight to 100% by weight, for example 50% by weight to 99% by weight, for example 50% by weight to 90% by weight, for example 50% by weight to 80% by weight, for example 50% by weight to 70% by weight, for example 50% by weight to 60% by weight, for example 60% by weight to 100% by weight, for example 60% by weight to 99% by weight, for example 60% by weight to 90% by weight, for example 60% by weight to 80% by weight, for example 60% by weight to 70% by weight, for example 70% by weight to 100% by weight %, such as 70% to 99% by weight, for example 70% to 90% by weight, for example 70% to 80% by weight, for example 80% to 100% by weight, such as 80% to 99% by weight, for example 80% to 90% by weight, for example 90% to 100% by weight, such as 90% to 99% by weight, for example 95% to 100% by weight, for example 95% to 99% by weight, for example 95% to 100% by weight, such as 95% to 99% by weight.

[0111] The second-stage ethylenically unsaturated monomer composition may optionally contain other ethylenically unsaturated monomers. The other ethylenically unsaturated monomers may include any ethylenically unsaturated monomer known in the art. Examples of other ethylenically unsaturated monomers that can be used in the second-stage ethylenically unsaturated monomer composition include, but are not limited to, the monomers described above with respect to the preparation of the polymerizable dispersant, as well as di(meth)acrylates and poly(ethylene glycol)(meth)acrylates. Such monomers, if present at all, may be present in an amount of from 1 wt% to 80 wt%, based on the total weight of the second stage ethylenically unsaturated monomer composition, such as from 1 wt% to 70 wt%, for example from 1 wt% to 60 wt%, such as from 1 wt% to 50 wt%, for example from 1 wt% to 40 wt%, such as from 1 wt% to 30 wt%, for example from 1 wt% to 20 wt%, such as from 1 wt% to 10 wt%, for example from 1 wt% to 5 wt%, such as from 5 wt% to 80 wt%, for example from 5 wt% to 70 wt%, for example from 5 wt% to 60 wt%, such as from 5 wt% to 50 wt%, for example from 5 wt% to 40 wt%, for example from 5 wt% to 30 wt%, such as from 5 wt% to 20 wt%, for example from 5 wt% to 10 % by weight, such as 10% to 80% by weight, for example 10% to 70% by weight, for example 10% to 60% by weight, such as 10% to 50% by weight, for example 10% to 40% by weight, such as 10% to 30% by weight, for example 10% to 20% by weight, such as 20% to 80% by weight, for example 20% to 70% by weight, for example 20% to 60% by weight, such as 20% to 50% by weight, for example 20% to 40% by weight, such as 20% to 30% by weight, for example 30% to 80% by weight, for example 30% to 70% by weight, for example 30% to 60% by weight, such as 30% to 50% by weight, for example 30% to 40% by weight.

[0112] The addition polymer may comprise a polymerization product comprising 10wt% to 90wt% of polymeric dispersant residue, for example 10wt% to 80wt%, such as 10wt% to 70wt%, for example 10wt% to 60wt%, such as 10wt% to 50wt%, for example 10wt% to 40wt%, such as 10wt% to 30wt%, for example 10wt% to 20wt%, such as 20wt% to 90wt%, for example 20wt% to 80wt%, for example 20wt% to 70wt%, for example 20wt% to 60wt%, such as 20wt% to 50wt%, for example 20wt% to 40wt%, such as 20wt% to 30wt%, for example 30wt% to 90wt%, for example 30wt% to 80wt%, for example 30wt% to 70% by weight, such as 30% to 60% by weight, for example 30% to 50% by weight, for example 30% to 40% by weight, for example 40% to 90% by weight, for example 40% to 80% by weight, for example 40% to 70% by weight, for example 40% to 60% by weight, for example 40% to 50% by weight, for example 50% to 90% by weight, for example 50% to 80% by weight, such as 50% to 70% by weight, for example 50% to 60% by weight, for example 60% to 90% by weight, for example 60% to 80% by weight, for example 60% to 70% by weight, for example 70% to 90% by weight, for example 70% to 80% by weight, for example 80% to 90% by weight, wherein the weight percentages are based on the total weight of the addition polymer.

[0113] The addition polymer may comprise a polymerization product comprising 10% to 90% by weight of a residue of the second stage ethylenically unsaturated monomer composition, wherein the residue of the second stage ethylenically unsaturated monomer composition is, for example, 10% to 80% by weight, such as 10% to 70% by weight, for example 10% to 60% by weight, such as 10% to 50% by weight, for example 10% to 40% by weight, such as 10% to 30% by weight, for example 10% to 20% by weight, such as 20% to 90% by weight, for example 20% to 80% by weight, such as 20% to 70% by weight, for example 20% to 60% by weight, such as 20% to 50% by weight, for example 20% to 40% by weight, such as 20% to 30% by weight, for example 30% to 90% by weight, for example 30% to 80% by weight. % by weight, such as 30% to 70% by weight, for example 30% to 60% by weight, for example 30% to 50% by weight, for example 30% to 40% by weight, such as 40% to 90% by weight, for example 40% to 80% by weight, for example 40% to 70% by weight, for example 40% to 60% by weight, such as 40% to 50% by weight, for example 50% to 90% by weight, for example 50% to 80% by weight, such as 50% to 70% by weight, for example 50% to 60% by weight, such as 60% to 90% by weight, for example 60% to 80% by weight, for example 60% to 70% by weight, such as 70% to 90% by weight, for example 70% to 80% by weight, for example 80% to 90% by weight, wherein the weight percentage is based on the total weight of the addition polymer.

[0114] According to the present disclosure, an addition polymer may comprise the polymerization product of a polymerizable dispersant and a second stage ethylenically unsaturated monomer composition, wherein the weight ratio of the second stage ethylenically unsaturated monomer composition to the polymerizable dispersant may be from 9:1 to 1:9, and the weight ratio may be, for example, from 9:1 to 1:4, such as from 9:1 to 3:7, for example, from 9:1 to 2:3, such as from 9:1 to 1:1, for example, from 9:1 to 3:2, such as from 9:1 to 7:3, for example, from 9:1 to 4:1, for example, from 4:1 to 1:9, for example, from 4:1 to 1:4, such as from 4:1 to 3:7, for example, from 4:1 to 2:3, for example 4:1~1:1, for example 4:1~3:2, for example 4:1~7:3, for example 4:1~9:1, for example 7:3~1:9, for example 7:3~1:4, for example 7:3~3:7, for example 7:3~2:3, for example 7:3~1:1, for example 7:3~3:2, for example 7:3~4:1, for example 7:3~9:1, for example 3:2~1:9, for example 3:2~1:4, for example 3:2~3:7, for example 3:2~2:3, for example 3:2~1:1, for example 3:2~7:3, for example 3:2~4:1, for example 3:2~9:1, For example, 1:1~1:9, for example, 1:1~1:4, for example, 1:1~3:7, for example, 1:1~2:3, for example, 1:1~3:2, for example, 1:1~7:3, for example, 1:1~4:1, for example, 1:1~9:1, for example, 2:3~1:9, for example, 2:3~1:4, for example, 2:3~3:7, for example, 2:3~1:1, for example, 2:3~3:2, for example, 9:1~7:3, for example, 2:3~4:1, for example, 2:3~9:1, for example, 3:7~1:9, for example, 3:7~1:4, for example, 3:7~2:3, for example, 3:7~1:1, for example, 3:7 to 3:2, for example, 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.

[0115] The addition polymer may contain active hydrogen functional groups, which may include hydroxyl groups, mercaptan groups, primary amine groups, and / or secondary amine groups.

[0116] The addition polymer may have a theoretical hydroxyl equivalent weight of from 120 g / OH to 310 g / OH, such as from 130 g / OH to 275 g / OH, such as from 140 g / OH to 200 g / OH, such as from 145 g / OH to 160 g / OH.

[0117] The addition polymer may have a theoretical hydroxy value of 190-400 mg KOH / gram addition polymer, e.g., 250-390 mg KOH / gram addition polymer, e.g., 320-380 mg KOH / gram addition polymer, e.g., 355-370 mg KOH / gram addition polymer. As used herein, the term "theoretical hydroxy value" typically refers to the number of milligrams of potassium hydroxide required to neutralize the acetic acid incorporated during the acetylation of one gram of a chemical containing a free hydroxyl group, and is determined herein by theoretical calculation of the number of free hydroxyl groups theoretically present in one gram of addition polymer.

[0118] According to the present disclosure, the addition polymer may have a z-average molecular weight of 500,000 g / mol to 5,000,000 g / mol, such as 1,400,000 g / mol to 2,600,000 g / mol, such as 1,800,000 g / mol to 2,200,000 g / mol, such as 1,500,000 g / mol to 1,700,000 g / mol, such as 750,000 g / mol to 950,000 g / mol. The z-average molecular weight can be measured by gel permeation chromatography using polystyrene standards using the same procedure as described above.

[0119] According to the present disclosure, the addition polymer may have a weight average molecular weight of 200,000 g / mol to 1,600,000 g / mol, such as 400,000 g / mol to 900,000 g / mol, such as 500,000 g / mol to 800,000 g / mol. The weight average molecular weight can be measured by gel permeation chromatography using polystyrene standards in the same manner as described above.

[0120] According to the present disclosure, an addition polymer may be nearly free, substantially free, or completely free of silicon. As used herein, "silicon" refers to elemental silicon or silicon-containing compounds, such as organosilicon compounds, including alkoxysilanes. As used herein, an addition polymer is "nearly free" of silicon if silicon is present in the addition polymer in an amount of less than 2 wt.%, based on the total weight of the addition polymer. As used herein, an addition polymer is "substantially free" of silicon if silicon is present in the addition polymer in an amount of less than 1 wt.%, based on the total weight of the addition polymer. As used herein, an addition polymer is "completely free" of silicon if no silicon is present in the addition polymer, i.e., 0 wt.%.

[0121] According to the present disclosure, addition polymers may be formed by a two-stage polymerization process. The first stage of the two-stage polymerization process involves forming a polymerizable dispersant from a first-stage ethylenically unsaturated monomer composition, as described above. The second stage of the two-stage polymerization process involves forming an addition polymer comprising the polymerization product of the polymerizable dispersant formed during the first stage and a second-stage ethylenically unsaturated monomer composition, as described above. The second stage of the polymerization process may include (a) dispersing the second-stage ethylenically unsaturated monomer composition and a free radical initiator in a dispersing medium comprising water in the presence of the at least partially neutralized polymerizable dispersant to form an aqueous dispersion, and (b) subjecting the aqueous dispersion to emulsion polymerization conditions, e.g., by heating in the presence of the free radical initiator, to polymerize the components and form an aqueous dispersion comprising the formed addition polymer. The polymerization time and temperature may depend, relative to the selected components and, in some cases, the scale of the reaction. For example, the polymerization may be carried out at 40°C to 100°C for 2 to 20 hours.

[0122] The free radical initiator utilized in the polymerization of the polymerizable dispersant and the second stage ethylenically unsaturated monomer composition may be selected from any of those used in aqueous addition polymerization techniques, including redox pair initiators, peroxides, hydroperoxides, peroxydicarbonates, azo compounds, and the like. The free radical initiator may be present in an amount of 0.01% to 5% by weight, such as 0.05% to 2.0% by weight, such as 0.1% to 1.5% by weight, based on the weight of the second stage ethylenically unsaturated monomer composition. A chain transfer agent soluble in the monomer composition, such as an alkyl mercaptan, e.g., tert-dodecyl mercaptan, 2-mercaptoethanol, isooctyl mercaptopropionate, n-octyl mercaptan, or 3-mercaptoacetic acid, may also be used in the polymerization of the polymerizable dispersant and the second stage ethylenically unsaturated monomer composition. Other chain transfer agents, such as ketones, e.g., methyl ethyl ketone, and chlorocarbons, e.g., chloroform, may also be used. When a chain transfer agent is present, its amount may be from 0.1% to 6.0% by weight, based on the weight of the second-stage ethylenically unsaturated monomer composition. Relatively high molecular weight multifunctional mercaptans may be substituted in whole or in part for the chain transfer agent. The molecular weight of these molecules may be, for example, from about 94 to 1,000 g / mol or more. The functionality may be from about 2 to about 4. When these multifunctional mercaptans are present, their amount may be from 0.1% to 6.0% by weight, based on the weight of the second-stage ethylenically unsaturated monomer composition.

[0123] Water may be present in the aqueous dispersion in an amount of 40% to 90% by weight, such as 40% to 75% by weight, such as 40% to 60% by weight, such as 50% to 90% by weight, such as 50% to 75% by weight, such as 50% to 60% by weight, such as 60% to 90% by weight, such as 60% to 75% by weight, such as 75% to 90% by weight, based on the total weight of the aqueous dispersion. The addition polymer may be added to the other components of the electrodepositable coating composition as an aqueous dispersion of the addition polymer.

[0124] In addition to water, the dispersion medium may further contain an organic cosolvent. The organic cosolvent may be at least partially soluble in water. Examples of such solvents include oxygenated organic solvents such as ethylene glycol, diethylene glycol, propylene glycol, and monoalkyl ethers of dipropylene glycol containing 1 to 10 carbon atoms in the alkyl group, such as the monoethyl and monobutyl ethers of these glycols. Examples of other at least partially water-miscible solvents include alcohols such as ethanol, isopropanol, butanol, and diacetone alcohol. When an organic cosolvent is used, the organic cosolvent may be present in an amount of less than 10% by weight, for example, less than 5% by weight, based on the total weight of the dispersion medium.

[0125] The addition polymer may be present in the electrodepositable coating composition in an amount of 0.01 wt % to 5 wt %, based on the total weight of resin solids of the electrodepositable coating composition, such as 0.01 wt % to 3 wt %, for example 0.01 wt % to 2 wt %, such as 0.01 wt % to 1.5 wt %, for example 0.01 wt % to 1 wt %, such as 0.01 wt % to 0.75 wt %, for example 0.1 wt % to 5 wt %, for example 0.1 wt % to 3 wt %, for example 0.1 wt % to 2 wt %, such as 0.1 wt % to 1.5 wt %, for example 0.1 wt % to 1 wt %, such as 0.1 wt % to 0.75 wt %, for example 0. It may be present in an amount of 3wt% to 5wt%, such as 0.3wt% to 3wt%, for example 0.3wt% to 2wt%, for example 0.3wt% to 1.5wt%, such as 0.3wt% to 1wt%, for example 0.3wt% to 0.75wt%, such as 0.5wt% to 5wt%, for example 0.5wt% to 3wt%, for example 0.5wt% to 2wt%, such as 0.5wt% to 1.5wt%, for example 0.5wt% to 1wt%, such as 0.5wt% to 0.75wt%, for example 1wt% to 5wt%, such as 1wt% to 3wt%, for example 1wt% to 2wt%, such as 1wt% to 1.5wt%.

[0126] Hydroxyl-Functional Addition Polymers As noted above, the organic resin component may comprise a hydroxyl-functional addition polymer, at least 70% of which contain constitutional units comprising Formula VIII. -[-C(R 1 )2-C(R 1 )(OH)-]- (VIII), In the formula, each R 1 is independently one of hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, alkylcycloalkyl, substituted alkylcycloalkyl, cycloalkylalkyl, substituted cycloalkylalkyl, aryl, substituted aryl, alkylaryl, substituted alkylaryl, cycloalkylaryl, substituted cycloalkylaryl, arylalkyl, substituted arylalkyl, arylcycloalkyl, or substituted arylcycloalkyl, where the percentages are based on all units of the hydroxyl-functional addition polymer. The addition polymer may contain hydroxyl functionality, but is different from the hydroxyl-functional addition polymer.

[0127] Non-limiting examples of suitable alkyl radicals are methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, amyl, hexyl, and 2-ethylhexyl.

[0128] Non-limiting examples of suitable cycloalkyl radicals include cyclobutyl, cyclopentyl and cyclohexyl.

[0129] Non-limiting examples of suitable alkylcycloalkyl radicals are methylenecyclohexane, ethylenecyclohexane, and propane-1,3-diylcyclohexane.

[0130] Non-limiting examples of suitable cycloalkylalkyl radicals are 2-, 3-, and 4-methyl, -ethyl, -propyl, -butylcyclohexan-1-yl.

[0131] Non-limiting examples of suitable aryl radicals include phenyl, naphthyl, and biphenylyl.

[0132] Non-limiting examples of suitable alkylaryl radicals are benzyl-[sic], ethylene-, and propane-1,3-diyl-benzene.

[0133] Non-limiting examples of suitable cycloalkylaryl radicals include 2-, 3-, and 4-phenylcyclohexan-1-yl.

[0134] Non-limiting examples of suitable arylalkyl radicals are 2-, 3-, and 4-methyl-, -ethyl-, -propyl-, and -butylphen-1-yl.

[0135] Non-limiting examples of suitable arylcycloalkyl radicals include 2-, 3-, and 4-cyclohexylphen-1-yl.

[0136] The above radical R 1 may be substituted. For this purpose, electron-withdrawing or electron-donating atoms or organic radicals may be used.

[0137] Examples of suitable substituents are halogen atoms (e.g., chlorine and fluorine), nitrile groups, nitro groups, partially or fully halogenated groups (e.g., chlorinated and / or fluorinated), alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl, and arylcycloalkyl radicals (including those exemplified above, especially tert-butyl), aryloxy, alkyloxy, and cycloalkyloxy radicals (especially phenoxy, naphthoxy, methoxy, ethoxy, propoxy, butyloxy, cyclohexyloxy, etc.). etc.), arylthio, alkylthio and cycloalkylthio radicals (especially phenylthio, naphthylthio, methylthio, ethylthio, propylthio, butylthio, cyclohexylthio etc.), hydroxyl groups, and / or primary, secondary and / or tertiary amino groups (especially 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, N-ethyl-N-methylamino).

[0138] R 1 may contain, consist essentially of, or consist only of hydrogen. For example, R 1 may contain hydrogen in at least 80% of the building blocks according to formula VIII, such as at least 90% of the building blocks, such as at least 92% of the building blocks, for example at least 95% of the building blocks, such as 100% of the building blocks.

[0139] The hydroxyl-functional addition polymer may comprise at least 70% of the units according to Formula VIII, based on all the units in the hydroxyl-functional addition polymer, such as at least 80%, such as at least 85%, such as at least 90%. The hydroxyl-functional addition polymer may comprise up to 100% of the units according to Formula VIII, based on all the units in the hydroxyl-functional addition polymer, such as up to 95%, such as up to 92%, such as up to 90%. The hydroxyl functional addition polymer may comprise constitutional units according to Formula VIII in an amount of from 70% to 95% of the hydroxyl functional addition polymer, such as from 80% to 95%, for example from 85% to 95%, for example from 90% to 95%, for example from 92% to 95%, for example from 70% to 92%, for example from 80% to 92%, for example from 85% to 92%, for example from 90% to 92%, for example from 70% to 90%, for example from 80% to 90%, for example from 85% to 90% of the hydroxyl functional addition polymer, said percentages being based on all constitutional units of the hydroxyl functional addition polymer.

[0140] According to the present disclosure, the hydroxyl-functional addition polymer may optionally further include constitutional units comprising the residue of a vinyl ester. The vinyl ester may include any suitable vinyl ester. For example, the vinyl ester may be represented by the formula C(R 1 )2==C(R 1 )(C(O)CH), wherein 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. Non-limiting examples of suitable vinyl esters include vinyl acetate, vinyl formate, or a combination thereof.

[0141] According to the present disclosure, a hydroxyl-functional addition polymer may be formed by polymerizing vinyl ester monomers to form an interpolymer comprising constitutional units comprising the residue of a vinyl ester, and then hydrolyzing the constitutional units comprising the residue of a vinyl ester of the interpolymer to form a hydroxyl-functional addition polymer. The vinyl ester residues may comprise 70% to 95% of the hydroxyl-functional addition polymer, such as 80% to 95%, for example 85% to 95%, for example 90% to 95%, for example 92% to 95%, for example 70% to 92%, for example 80% to 92%, for example 85% to 92%, for example 90% to 92%, for example 70% to 90%, for example 80% to 90%, for example 85% to 90%, where the percentages are based on the total constitutional units of the interpolymer.

[0142] According to the present disclosure, the hydroxyl functional addition polymer may have a theoretical hydroxyl equivalent weight of from 30 g / OH to 200 g / OH, such as from 30 g / OH to 100 g / OH, such as from 30 g / OH to 60 g / OH, such as from 30 g / OH to 50 g / OH, such as from 35 g / OH to 200 g / OH, such as from 35 g / OH to 100 g / OH, such as from 35 g / OH to 60 g / OH. The hydroxyl functional polymer may have a theoretical hydroxyl equivalent weight of from 35 g / OH to 50 g / OH, for example from 40 g / OH to 200 g / OH, for example from 40 g / OH to 100 g / OH, for example from 40 g / OH to 60 g / OH, for example from 40 g / OH to 50 g / OH, for example from 44 g / OH to 200 g / OH, for example from 44 g / OH to 100 g / OH, for example from 44 g / OH to 60 g / OH, for example from 44 g / OH to 50 g / OH. As used herein, the term "theoretical hydroxyl equivalent weight" refers to the weight in grams of the hydroxyl functional addition polymer resin solids divided by the theoretical equivalent of hydroxyl groups present in the hydroxyl functional addition polymer and may be calculated according to the following formula (a):

number

[0143] In accordance with the present disclosure, the hydroxyl functional addition polymer may have a theoretical hydroxy value of from 1,000 to 1,300 mg KOH / gram of addition polymer, such as from 1,000 to 1,200 mg KOH / gram of addition polymer, for example from 1,000 to 1,150 mg KOH / gram of addition polymer, for example from 1,100 to 1,300 mg KOH / gram of addition polymer, for example from 1,100 to 1,200 mg KOH / gram of addition polymer, for example from 1,100 to 1,150 mg KOH / gram of addition polymer, for example from 1,150 to 1,300 mg KOH / gram of addition polymer, for example from 1,150 to 1,200 mg KOH / gram of addition polymer.

[0144] According to the present disclosure, the hydroxyl-functional addition polymers have a number average molecular weight (M) as determined by gel permeation chromatography using polystyrene standards. n ) may be 5,000g / mol to 500,000g / mol, for example, 5,000g / mol to 300,000g / mol, for example, 5,000g / mol to 200,000g / mol, for example, 5,000g / mol to 125,000g / mol, for example, 25,000g / mol to 500,000g / mol, for example, 25,000g / mol to 300,000g / mol, for example, 25,000g / mol to 200,000g / mol, for example, 25,000g / mol to 125,000g / mol, for example, 75, 000g / mol to 500,000g / mol, for example 75,000g / mol to 300,000g / mol, for example 75,000g / mol to 200,000g / mol, for example 75,000g / mol to 125,000g / mol, for example 100,000g / mol to 500,000g / mol, for example 100,000g / mol to 300,000g / mol, for example 100,000g / mol to 200,000g / mol, for example 100,000g / mol to 125,000g / mol.

[0145] According to the present disclosure, the hydroxyl functional addition polymer may have a weight average molecular weight of 5,000 g / mol to 500,000 g / mol, such as 5,000 g / mol to 300,000 g / mol, for example 5,000 g / mol to 200,000 g / mol, for example 5,000 g / mol to 125,000 g / mol, for example 25,000 g / mol to 500,000 g / mol, for example 25,000 g / mol to 300,000 g / mol, for example 25,000 g / mol to 200,000 g / mol, for example It may be 25,000 g / mol to 125,000 g / mol, for example, 75,000 g / mol to 500,000 g / mol, for example, 75,000 g / mol to 300,000 g / mol, for example, 75,000 g / mol to 200,000 g / mol, for example, 75,000 g / mol to 125,000 g / mol, for example, 100,000 g / mol to 500,000 g / mol, for example, 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.

[0146] As used herein, unless otherwise defined, "number average molecular weight (M n ) and "weight average molecular weight (M w ) and "number average molecular weight (M n ) and weight average molecular weight (M w ) and was determined by gel permeation chromatography under the conditions shown below. Gel permeation chromatography was performed using a Waters 2695 separation module equipped with a Waters 410 differential refractometer (RI detector), polystyrene standards with molecular weights ranging from approximately 500 g / mol to 900,000 g / mol, dimethylformamide (DMF) containing 0.05 M lithium bromide (LiBr) at a flow rate of 0.5 mL / min, and an Asahipak GF-510 HQ column (1 column).

[0147] According to the present disclosure, a 4 wt % solution of the hydroxyl functional addition polymer in water may have a viscosity measured at 20°C using a Brookfield synchronous motor rotational viscometer of 10-110 cP, such as 10-90 cP, for example 10-70 cP, such as 10-50 cP, for example 10-40 cP, such as 15-110 cP, for example 15-90 cP, for example 15-70 cP, for example 15-60 cP, for example 15-50 cP, for example 15-40 cP, such as 20-110 cP, for example 20-90 cP, for example 20-70 cP, for example 20-60 cP, for example 20-50 cP, for example 20-40 cP.

[0148] According to the present disclosure, the above-described hydroxyl-functional addition polymer may be present in the electrodepositable coating composition in an amount of at least 0.01 wt.%, such as at least 0.1 wt.%, for example at least 0.3 wt.%, such as at least 0.5 wt.%, for example at least 0.75 wt.%, such as 1 wt.%, based on the total weight of resin solids of the electrodepositable coating composition. The above-described hydroxyl-functional addition polymer may be present in the electrodepositable coating composition in an amount of 5 wt.% or less, such as 3 wt.% or less, for example 2 wt.% or less, for example 1.5 wt.% or less, for example 1 wt.% or less, for example 0.75 wt.% or less, based on the total weight of resin solids of the electrodepositable coating composition. The hydroxyl functional addition polymer may be present in the electrodepositable coating composition in an amount of 0.01 wt.% to 5 wt.%, based on the total weight of resin solids of the electrodepositable coating composition, for example, 0.01 wt.% to 3 wt.%, such as 0.01 wt.% to 2 wt.%, for example, 0.01 wt.% to 1.5 wt.%, such as 0.01 wt.% to 1 wt.%, for example, 0.01 wt.% to 0.75 wt.%, such as 0.1 wt.% to 5 wt.%, for example, 0.1 wt.% to 3 wt.%, for example, 0.1 wt.% to 2 wt.%, for example, 0.1 wt.% to 1.5 wt.%, such as 0.1 wt.% to 1 wt.%, for example, 0.1 wt.% to 0.75 wt.%, or For example it may be present in an amount of 0.3wt% to 5wt%, such as 0.3wt% to 3wt%, for example 0.3wt% to 2wt%, for example 0.3wt% to 1.5wt%, such as 0.3wt% to 1wt%, for example 0.3wt% to 0.75wt%, such as 0.5wt% to 5wt%, for example 0.5wt% to 3wt%, for example 0.5wt% to 2wt%, such as 0.5wt% to 1.5wt%, for example 0.5wt% to 1wt%, such as 0.5wt% to 0.75wt%, for example 1wt% to 5wt%, for example 1wt% to 3wt%, for example 1wt% to 2wt%, such as 1wt% to 1.5wt%.

[0149] cellulose As described above, the organic resin component 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 carboxymethyl cellulose and its salts (CMC). CMC is a cellulose ether in which a portion of the hydroxyl groups on the anhydroglucose ring are substituted with carboxymethyl groups. The degree of substitution of the carboxymethyl groups can range from 0.4 to 3. Because CMC is a long-chain polymer, its viscosity in aqueous solution depends on its molecular weight and can vary from 50,000 to 2,000,000 g / mol (weight average). The carboxymethyl cellulose may have a weight average molecular weight of at least 50,000 g / mol, such as at least 100,000 g / mol, for example at least 200,000 g / mol, for example, a weight average molecular weight of 50,000 g / mol to 1,000,000 g / mol, 100,000 g / mol to 500,000 g / mol, or 200,000 g / mol to 300,000 g / mol. The degree of substitution and viscosity of aqueous solutions can be measured according to ASTM D 1439-03. The molecular weight is typically estimated from the viscosity of a standard CMC solution.

[0150] The water-soluble cellulose derivative may be present in the electrodepositable coating composition in an amount of at least 0.001 wt %, such as at least 0.05 wt %, for example, from 0.001 wt % to 10 wt %, or from 0.05 wt % to 2 wt %, based on the total weight of resin solids.

[0151] Polyvinylformamide polymer As mentioned above, the organic resin component may include a polyvinylformamide polymer. The polyvinylformamide polymer may be unhydrolyzed, partially hydrolyzed, or completely hydrolyzed. Hydrolysis of the formamide groups yields primary amine groups, and complete hydrolysis of the polyvinylformamide polymer yields poly(vinylamine). Hydrolyzed polyvinylformamide polymers are commercially available from BASF under the trademark "LUAMIN®" and have a variety of weight-average molecular weights (from about 340,000 daltons to less than 10,000 daltons) and degrees of hydrolysis (10%, 30%, 90%). The unhydrolyzed or hydrolyzed polyvinylformamide polymer may also contain monomer units other than vinylamide and vinylamine monomer units. In one embodiment of such a copolymer, vinylformamide may be copolymerized with vinyl acetate. Hydrolysis of the resulting copolymer may yield vinyl alcohol and vinylamine monomer units. In one embodiment, the polyvinylformamide polymer includes only vinylamide and vinylamine monomer units (i.e., the polyvinylformamide polymer is a homopolymer of vinylformamide or an at least partially hydrolyzed homopolymer of vinylformamide).

[0152] The electrodeposition coating composition generally contains less than 1 weight percent of the unhydrolyzed or hydrolyzed polyvinyl formamide polymer. For example, the electrodeposition coating composition may contain at least about 25 ppm by weight of the unhydrolyzed or hydrolyzed polyvinyl formamide polymer; in other examples, the aqueous electrodeposition coating composition may contain at least about 50 ppm by weight of the unhydrolyzed or hydrolyzed polyvinyl formamide polymer. For example, the aqueous electrodeposition coating composition may contain up to about 1000 ppm by weight of the unhydrolyzed or hydrolyzed polyvinyl formamide polymer; in other examples, the aqueous electrodeposition coating composition may contain up to about 100 ppm by weight of the unhydrolyzed or hydrolyzed polyvinyl formamide polymer. Determining the optimal amount of unhydrolyzed or hydrolyzed polyvinyl formamide polymer for a particular aqueous electrodeposition coating composition is straightforward, and generally, satisfactory results can be achieved with an amount of unhydrolyzed or hydrolyzed polyvinyl formamide polymer of less than 1000 ppm by weight, based on the weight of the aqueous electrodeposition coating composition.

[0153] Cationic epoxy microgel According to the present disclosure, the organic resin component may include a cationic epoxy microgel. The term "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 crosslinker in an aqueous medium. The dispersion step can be accomplished by adding the polyepoxide-amine reaction product to a mixture of water and an acid at an elevated temperature, preferably between 100°C and 150°C, to form a cationic dispersion of the resin in water. Typically, the resulting dispersion will have a solids content of approximately 20-50% by weight and a degree of neutralization of 20-100% of the theoretical neutralization. The acid can be organic, such as formic acid, lactic acid, or acetic acid, or inorganic, such as phosphoric acid or sulfamic acid. Blends of acids, including blends of organic and inorganic acids, can also be used. The degree of neutralization varies depending on the specific reaction product; typically, only enough acid is added to stabilize the resulting microgel dispersion. The phrase "cationic polyepoxide-amine reaction products containing primary and / or secondary amine groups" includes primary and secondary amine groups and their acid salts.

[0154] Polyamine-dialdehyde adduct According to the present disclosure, the crater control additive may include a polyamine-dialdehyde adduct comprising the polymerization product of a polyamine and a dialdehyde, or may optionally include a polyamine-dialdehyde adduct consisting solely of the polymerization product of a polyamine and a dialdehyde, or may optionally include a polyamine-dialdehyde adduct consisting essentially of the polymerization product of a polyamine and a dialdehyde. The polyamine and dialdehyde may be polymerized to form the polymerization product. As used herein, "polyamine" includes compounds containing at least two amino groups, including primary or secondary amino groups. As used herein, a "primary amino group" refers to a derivative of ammonia in which one hydrogen atom is replaced by an alkyl or aryl group, and a "secondary amino group" refers to a derivative of ammonia in which two hydrogen atoms are replaced by alkyl or aryl groups. As used herein, "alkyl" refers to a hydrocarbon chain that may be linear or branched and may contain one or more hydrocarbon rings that are not aromatic. As used herein, "aryl" refers to a hydrocarbon having a delocalized conjugated π-system with alternating single and double bonds between carbon atoms forming one or more coplanar hydrocarbon rings.

[0155] According to the present disclosure, the polyamine may include a cationic amine-functionalized resin, a polyetheramine, or a combination thereof. The cationic amine-functionalized resin may be derived from a polyepoxide. For example, the cationic amine-functionalized resin may be prepared by reacting a polyepoxide with a polyhydroxyl-containing material selected from an alcoholic hydroxyl-containing material and a phenolic hydroxyl-containing material to chain extend or build the molecular weight of the polyepoxide. Other hydroxyl-containing materials that may constitute the cationic amine-functionalized resin may include adducts of phenolic hydroxyl-containing materials with alkylene oxides. The reaction product can then be reacted with a cationic salt group-forming agent to obtain the cationic amine-functionalized resin.

[0156] According to the present disclosure, the polyamine may also include a polyetheramine, which may have propylene oxide, ethylene oxide, or a mixture thereof repeating units in its structure (such as one of the Jeffamine series products available from Huntsman). Examples of such polyetheramines include aminated propoxylated pentaerythritol, such as Jeffamine XTJ-616, and those represented by formulas (IX)-(XI).

[0157] According to formula (IX) of the present disclosure, the polyetheramine may comprise or represent: [ka] Here, y = 0 to 39, and x + z = 1 to 68.

[0158] Suitable polyetheramines of formula (IX) include, but are not limited to, amine-terminated polyethylene glycols such as Huntsman's Jeffamine ED series, e.g., Jeffamine HK-511, Jeffamine ED-600, Jeffamine ED-900, and Jeffamine ED-2003, and amine-terminated polypropylene glycols such as Huntsman's Jeffamine D series, e.g., Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, and Jeffamine D-4000.

[0159] According to formula (X) of the present disclosure, the polyetheramine may comprise or represent: [ka] wherein each p is independently 2 or 3.

[0160] Suitable polyetheramines represented by formula (X) include, but are not limited to, amine-terminated polyethylene glycol-based diamines such as the Jeffamine EDR series from Huntsman, e.g., Jeffamine EDR-148 and Jeffamine EDR-176.

[0161] According to formula (XI) of the present disclosure, the polyetheramine may comprise or represent: [ka] Here, R is H or C2H5, m=0 or 1, and a+b+c=5 to 85.

[0162] Suitable polyetheramines of formula (XI) include, but are not limited to, amine-terminated propoxylated trimethylolpropane or glycerol, such as Huntsman's Jeffamine T series, including Jeffamine T-403, Jeffamine T-3000, and Jeffamine T-5000.

[0163] The z-average molecular weight (M z As used herein, the "z-average molecular weight (M)" may be from 5,000 g / mol to 300,000 g / mol, such as from 7,000 g / mol to 100,000 g / mol, such as from 10,000 g / mol to 15,000 g / mol. z The term "z-average molecular weight (M)" refers to the z-average molecular weight (M) determined by gel permeation chromatography using a Waters 2695 Separation Module equipped with a Waters 410 Differential Refractometer (RI detector), polystyrene standards with molecular weights ranging from approximately 500 g / mol to 900,000 g / mol, eluted with dimethylformamide (DMF) containing lithium bromide (LiBr) at a flow rate of 0.5 mL / min, and one Asahipak GF-510 HQ column for separation.z ) means

[0164] The amine equivalent weight of the polyamine may be from 200 g / amine to 5,000 g / amine, such as from 400 g / amine to 2,000 g / amine, such as from 450 g / amine to 600 g / amine. As used herein, "amine equivalent weight" is determined by dividing the molecular weight of the amine-containing compound by the number of amino groups present in the polyamine.

[0165] As described above, according to the present disclosure, a polyamine may be polymerized with a dialdehyde to form a polyamine-dialdehyde adduct. The dialdehyde may contain two aldehyde functional groups per molecule. As used herein, an "aldehyde functional group" includes the structure R-CHO, in which the carbonyl carbon atom is bonded to a hydrogen atom and an alkyl group represented by the letter R. Suitable dialdehyde compounds include, but are not limited to, glyoxal, glutaraldehyde, and combinations thereof.

[0166] According to the present disclosure, the polymerization of polyamines and dialdehydes to form polyamine-dialdehyde adducts may be carried out in an aqueous medium at a pH of less than 7, such as less than 6.5, and may be carried out at a pH of at least 2, such as at least 5. According to the present disclosure, the polymerization of polyamines and dialdehydes to form polyamine-dialdehyde adducts may be carried out in an aqueous medium at a pH of 2 to 7, such as a pH of 5 to 6.5.

[0167] According to the present disclosure, the polyamine-dialdehyde adduct may have a z-average molecular weight (Mz) of 100,000 g / mol to 1,000,000 g / mol, such as 300,000 g / mol to 700,000 g / mol, such as 400,000 g / mol to 600,000 g / mol. Those skilled in the art will recognize the inherent limitations in measuring the molecular weight of high molecular weight compounds, e.g., compounds having a molecular weight greater than 900,000 g / mol. Therefore, the theoretical z-average molecular weight (Mz) of the polyamine-dialdehyde adduct may be calculated using the following formula: z Although the stoichiometric ratio (mM) is expected to increase as the dialdehyde to polyamine ratio approaches 1 (i.e., when the dialdehyde to polyamine ratio is ≤ 1), the measured molecular weight may not reflect this due to limitations in the measurement standards. This result is expected not because the molecular weight of the adduct does not increase as the stoichiometry increases, but because it is difficult to measure the molecular weight of such high molecular weight compounds using current analytical methods. Specifically, because GPC is a type of size-exclusion chromatography, higher molecular weight polymers elute from the column faster than lower molecular weight polymers. Once the majority of the polymer exceeds a certain molecular weight, the polymer molecules elute from the column too quickly to accurately measure the molecular weight.

[0168] As discussed in more detail below, the polyamine-dialdehyde adducts can function in the electrodepositable coating composition as a primary vehicle, as an additive added to the electrodepositable coating composition as a preblend component of the resin blend, or as a combination of primary vehicle and additive.

[0169] As noted above, in accordance with the present disclosure, the polyamine-dialdehyde adduct can function as a primary vehicle in the electrodepositable coating composition. In such examples, the polyamine-dialdehyde adduct can be present in the electrodepositable coating composition in an amount of 50% to 95% by weight, such as 70% to 90%, e.g., 75% to 85%, based on the total resin blend solids.

[0170] According to the present disclosure, the polyamine-dialdehyde adduct can function as a primary vehicle. According to the present disclosure, the stoichiometric ratio of aldehyde functional groups of the dialdehyde compound to primary and / or secondary amino functional groups from the polyamine can be 2:1 to 20:1, such as 3:1 to 15:1, for example, 4:1 to 14:1.

[0171] In accordance with the present disclosure, the polyamine-dialdehyde adduct may also function as an additive in the electrodepositable coating composition. In such examples, in accordance with the present disclosure, the polyamine-dialdehyde adduct may be present in the electrodepositable coating composition in an amount of 0.2% to 20% by weight based on the total weight of resin blend solids, such as 0.5% to 15%, such as 0.75% to 10%, such as 1% to 4%.

[0172] According to the present disclosure, the polyamine-dialdehyde adduct can function as an additive. In such examples, the stoichiometric ratio of aldehyde functional groups from the dialdehyde compound to primary and / or secondary amino functional groups from the polyamine can be 2:10 to 1:1, such as 3:10 to 9:10, such as 5:10 to 8:10, or such as 5:10 to 7:10. As the stoichiometric ratio of aldehyde functional groups to amino functional groups increases, the molecular weight of the resulting polyamine-dialdehyde adduct increases accordingly, assuming a constant number of amino groups per polyamine molecule.

[0173] Polyetheramine Adduct According to the present disclosure, the electrodepositable coating composition may further comprise a polyetheramine adduct, which comprises an ungelled ionic reaction product prepared from reactants comprising (a) an epoxy-functional material or a reaction product prepared from reactants comprising (1) a polyol and (2) an epoxy-functional material, and (b) a polyetheramine.

[0174] Examples of suitable epoxy-functional materials useful for forming the ungelled ionic reaction product include those containing at least one epoxy group in the molecule, such as di- or polyglycidyl ethers of polyhydric alcohols, e.g., polyglycidyl ether of bisphenol A. Suitable epoxy-functional materials may have an epoxy equivalent weight ranging from about 90 to about 2000, as determined 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 may be combined or reacted with the above-described polyester to form the epoxy-functional polyester.

[0175] Examples of suitable polyols useful in forming the ungelled ionic reaction product include resorcinol, dihydroxybenzene, aliphatic, alicyclic, or araraphatic hydroxyl-containing compounds, such as ethylene glycol, propylene glycol, bisphenol A, dihydroxycyclohexane, dimethylolcyclohexane, or combinations thereof. The polyol may be present in the polyetheramine adduct in an amount of about 0% to 20% by weight, such as 0% to 15% by weight, based on the total weight of the reactants forming the polyether reaction product.

[0176] According to the present disclosure, polyetheramine adducts can be formed by reacting the ungelled ionic reaction product with at least one polyetheramine, which can be the same as those described above (e.g., one of the Jeffamine series products available from Huntsman Corporation), characterized by propylene oxide, ethylene oxide, or mixed repeat units in their respective structures. Examples of such polyetheramines include aminated propoxylated pentaerythritol, such as Jeffamine XTJ-616, and those represented by formulas (IX)-(XI) above.

[0177] Further examples of polyetheramine adducts include those described in U.S. Pat. Nos. 4,420,574 and 4,423,166, which are incorporated herein by reference.

[0178] The polyetheramine adduct may have a polyalkylene oxide content, such as polyethylene oxide, polypropylene oxide, polybutylene oxide, etc., of at least 50 wt.%, such as at least 60 wt.%, such as at least 70 wt.%, such as at least 80 wt.%, such as at least 90 wt.%, based on the total weight of the polyetheramine adduct.

[0179] The polyetheramine adduct may have a weight average molecular weight of at least 1,000 g / mol, such as at least 3,000 g / mol, for example at least 10,000 g / mol, such as at least 30,000 g / mol, for example at least 50,000 g / mol, such as at least 75,000 g / mol, for example at least 100,000 g / mol, such as at least 125,000 g / mol. The polyetheramine adduct may have a weight average molecular weight of 500,000 g / mol or less, such as 400,000 g / mol or less, for example 300,000 g / mol or less, for example 250,000 g / mol or less, such as 200,000 g / mol or less, for example 150,000 g / mol or less, such as 100,000 g / mol or less, for example 50,000 g / mol or less, such as 25,000 g / mol or less, for example 10,000 g / mol or less, for example 8,000 g / mol or less. The polyetheramine adduct may have a weight average molecular weight of 1,000 g / mol to 500,000 g / mol, for example, 1,000 g / mol to 400,000 g / mol, for example, 1,000 g / mol to 300,000 g / mol, for example, 1,000 g / mol to 250,000 g / mol, for example, 1,000 g / mol to 200,000 g / mol, for example, 1,000 g / mol to 150,000 g / mol, for example, 1,000 g / mol to 100,000 g / mol, for example, 1,000 g / mol to 50,000 g / mol, for example, 1,000 g / mol to 25 ,000g / mol, for example 1,000g / mol to 10,000g / mol, for example 1,000g / mol to 8,000g / mol, for example 3,000g / mol to 500,000g / mol, for example 3,000g / mol to 400,000g / mol, for example 3,000g / mol to 300,000g / mol, for example 3,000g / mol to 250,000g / mol, for example 3,000g / mol to 200,000g / mol, for example 3,000g / mol to 150,000g / mol, for example 3,000g / mol to 100,000g / mol, for example 3,000g / mol to 50,000g / mol, for example 3,000g / mol to 25,000g / mol, for example 3,000g / mol to 10,000g / mol, for example 3,000g / mol to 8,000g / mol, for example 10,000g / mol to 500,000g / mol, for example 10,000g / mol to 400,000g / mol, for example 10,000g / mol to 300,000g / mol, for example 10,000g / mol to 250,000g / mol, for example 10,000g / mol to 200,000g / mol, For example, 10,000g / mol to 150,000g / mol, for example, 10,000g / mol to 100,000g / mol, for example, 10,000g / mol to 50,000g / mol, for example, 10,000g / mol to 25,000g / mol, for example, 30,000g / mol to 500,000g / mol, for example, 30,000g / mol to 400,000g / mol, for example, 30,000g / mol to 300,000g / mol, for example, 30,000g / mol to 250,000g / mol, for example, 30,000g / mol to 20 0,000g / mol, for example 30,000g / mol to 150,000g / mol, for example 30,000g / mol to 100,000g / mol, for example 30,000g / mol to 50,000g / mol, for example 50,000g / mol to 500,000g / mol, for example 50,000g / mol to 400,000g / mol, for example 50,000g / mol to 300,000g / mol, for example 50,000g / mol to 250,000g / mol, for example 50,000g / mol to 200,000g / mol, for example 5 0,000g / mol to 150,000g / mol, for example 50,000g / mol to 100,000g / mol, for example 75,000g / mol to 500,000g / mol, for example 75,000g / mol to 400,000g / mol, for example 75,000g / mol to 300,000g / mol, for example 75,000g / mol to 250,000g / mol, for example 75,000g / mol to 200,000g / mol, for example 75,000g / mol to 150,000g / mol, for example 75,000g / mol to 100,000g / mol, for example 100,000g / mol to 500,000g / mol, for example 100,000g / mol to 400,000g / mol, for example 100,000g / mol to 300,000g / mol, for example 100,000g / mol to 250,000g / mol, for example 100,000g / mol to 200,000g / mol, for example 100,000g / mol to 150,000g / mol , for example, 125,000 g / mol to 500,000 g / mol, for example, 125,000 g / mol to 400,000 g / mol, for example, 125,000 g / mol to 300,000 g / mol, for example, 125,000 g / mol to 250,000 g / mol, for example, 125,000 g / mol to 200,000 g / mol, for example, 125,000 g / mol to 150,000 g / mol.

[0180] The polyetheramine adduct may be present in the electrodepositable coating and / or electrodepositable coating composition in an amount of at least 3 wt%, such as at least 5 wt%, for example at least 10 wt%, such as at least 15 wt%, for example at least 20 wt%, such as at least 25 wt%, based on the total weight of the electrodepositable binder. The polyetheramine adduct may be present in the electrodepositable coating and / or electrodepositable coating composition in an amount of 35 wt% or less, such as 30 wt% or less, based on the total weight of the electrodepositable binder, for example 25 wt% or less, such as 20 wt% or less, for example 15 wt% or less, such as 10 wt% or less, for example 5 wt% or less. The polyetheramine adduct may be present in the electrodepositable coating and / or electrodepositable coating composition in an amount of 3 wt.% to 35 wt.%, based on the total weight of the electrodepositable binder, for example 3 wt.% to 30 wt.%, such as 3 wt.% to 25 wt.%, for example 3 wt.% to 20 wt.%, such as 3 wt.% to 15 wt.%, for example 3 wt.% to 10 wt.%, such as 3 wt.% to 5 wt.%, for example 5 wt.% to 35 wt.%, for example 5 wt.% to 30 wt.%, such as 5 wt.% to 25 wt.%, for example 5 wt.% to 20 wt.%, such as 5 wt.% to 15 wt.%, for example It may be present in an amount of, for example, 5% to 10% by weight, such as 10% to 35% by weight, for example 10% to 30% by weight, for example 10% to 25% by weight, such as 10% to 20% by weight, for example 10% to 15% by weight, such as 15% to 35% by weight, for example 15% to 30% by weight, for example 15% to 25% by weight, such as 15% to 20% by weight, for example 20% to 35% by weight, for example 20% to 30% by weight, for example 20% to 25% by weight, such as 25% to 35% by weight, for example 25% to 30% by weight.

[0181] Further components of the electrodeposition coating and / or electrodepositable coating composition The electrodeposition coating and / or electrodepositable coating composition may optionally include one or more additional ingredients in addition to the components described above.

[0182] The electrodeposition coating and / or electrodepositable composition may optionally include a corrosion inhibitor. Any suitable corrosion inhibitor may be used. For example, the corrosion inhibitor may include a corrosion inhibitor containing yttrium, lanthanum, cerium, calcium, an azole, or any combination thereof.

[0183] Non-limiting examples of suitable azoles include benzotriazole, 5-methylbenzotriazole, 2-aminothiazole, and salts thereof.

[0184] The corrosion inhibitor(s), if present at all, may be present in the electrodeposited coating and / or electrodepositable coating composition in an amount of at least 0.001 wt.%, such as at least 5 wt.%, based on the total weight of the electrodeposited coating and / or the total solids weight of the electrodepositable coating composition. The corrosion inhibitor(s), if present at all, may be present in the electrodepositable coating composition in an amount of 25 wt.% or less, such as 15 wt.% or less, such as 10 wt.% or less, based on the total weight of the electrodeposited coating or the total solids weight of the electrodepositable coating composition. The corrosion inhibitor(s), if present at all, may be present in the electrodepositable coating composition in an amount of 0.001 wt. % to 25 wt. %, such as 0.001 wt. % to 15 wt. %, such as 0.001 wt. % to 10 wt. %, such as 5 wt. % to 25 wt. %, such as 5 wt. % to 15 wt. %, such as 5 wt. % to 10 wt. %, based on the total weight of the electrodepositable coating and / or the total solids weight of the electrodepositable coating composition.

[0185] Alternatively, the electrodeposition coating and / or electrodepositable coating composition may be little, substantially free, or completely free of corrosion inhibitors.

[0186] According to the present disclosure, the electrodeposition coating and / or electrodepositable coating composition may contain other optional components, such as various additives, such as fillers, plasticizers, antioxidants, biocides, ultraviolet absorbers and stabilizers, hindered amine light stabilizers, defoamers, bactericides, dispersing aids, flow control agents, surfactants, wetting agents, or combinations thereof, as desired. Alternatively, the electrodeposition coating and / or electrodepositable coating composition may be completely free of these optional components, i.e., the optional components are not present in the electrodeposition coating and / or electrodepositable coating composition. The above-mentioned other additives may be present in the electrodeposition coating and / or electrodepositable coating composition in an amount of 0.01% to 3% by weight, based on the total weight of the resin solids of the electrodeposition coating and / or electrodepositable coating composition.

[0187] The electrodeposition coating and / or electrodepositable coating composition may optionally further comprise a flame-retardant pigment. As used herein, "flame-retardant pigment" refers to a pigment that contributes to the flame retardancy of the coating.

[0188] The flame retardant pigment may comprise an inorganic pigment, a mineral, or a combination thereof.

[0189] As used herein, the term "inorganic" refers to materials that do not contain carbon atoms.

[0190] Non-limiting examples of inorganic pigments or minerals include metal hydroxides such as aluminum hydroxide, aluminum oxide or its hydrates, zinc compounds such as magnesium hydroxide, zinc borate or zinc hydroxystannate, metal borates, titanium dioxide, barium sulfate, geopolymers such as alkali aluminosilicates, boron compounds such as huntite, hydromagnesite, red phosphorus, borates, organic layered silicates, wollastonite, carbonates such as calcium carbonate, magnesium carbonate, iron oxide, lead oxide, strontium chromate, barium sulfate, boron nitride, silicon nitride, aluminum nitride, boron arsenide, silicon dioxide, titanium oxide, zinc oxide, nickel oxide, copper oxide, tin oxide, silicon carbide, agate, emery, diamond, silver, zinc, copper, gold, carbonyl iron, copper, zinc, aluminum, clay, colored pigments such as cadmium yellow, cadmium red, chrome yellow, or combinations thereof.

[0191] The flame retardant pigment may have at least one average particle size reported by the manufacturer of 0.01 microns to 100 microns, such as 0.01 microns to 50 microns, for example, 0.01 microns to 40 microns, for example, 0.01 microns to 25 microns, for example, 2 microns to 100 microns, for example, 2 microns to 50 microns, for example, 2 microns to 40 microns, for example, 2 microns to 25 microns, for example, 10 microns to 100 microns, for example, 10 microns to 50 microns, for example, 10 microns to 40 microns, for example, 10 microns to 25 microns. Suitable methods for measuring average particle size include, for example, measurement using an instrument such as a Quanta 250 FEG SEM or equivalent.

[0192] The flame-retardant pigment may be present in the electrodeposition coating and / or electrodepositable coating composition at a flame-retardant pigment to binder (P:B) ratio of at least 0.01:1, such as at least 0.05:1, such as at least 0.1:1, such as at least 0.12:1, such as at least 0.15:1, such as at least 0.17:1. The flame-retardant pigment may be present in the flame-retardant electrodepositable coating composition at a flame-retardant pigment to binder (P:B) ratio of less than 0.2:1, such as at most 0.17:1, such as at most 0.15:1, such as at most 0.12:1, such as at most 0.1:1, such as at most 0.05:1. The flame retardant pigment may be present in the flame retardant electrodepositable coating composition in a flame retardant pigment to binder (P:B) ratio of 0.01:1 to less than 0.2:1, such as 0.01:1 to 0.17:1, for example 0.01:1 to 0.15:1, for example 0.01:1 to 0.12:1, for example 0.01:1 to 0.1:1, for example 0.01:1 to 0.05:1, for example 0.05 to less than 0.2:1, for example 0.05:1 to 0.17:1, for example 0.05:1 to 0.15:1, for example 0.05: It may be present at 1 to 0.12:1, such as 0.05:1 to 0.1:1, for example 0.1:1 to less than 0.2:1, for example 0.1:1 to 0.17:1, for example 0.1:1 to 0.15:1, for example 0.1:1 to 0.12:1, for example 0.12:1 to less than 0.2:1, for example 0.12:1 to 0.17:1, for example 0.12:1 to 0.15:1, for example 0.15:1 to less than 0.2:1, for example 0.15:1 to 0.17:1, for example 0.17:1 to less than 0.2:1.

[0193] The electrodeposition coating and / or electrodepositable coating composition may optionally further comprise a binder comprising a hybrid organic-inorganic material. As used herein, the term "hybrid organic-inorganic material" refers to a material that is partially organic and contains at least one other atom other than hydrogen, oxygen, and / or nitrogen, such as a halogen, sulfur, phosphorus, silicon, etc., excluding melamine derivatives containing such atoms.

[0194] The hybrid organic-inorganic material can contribute to the flame retardancy of coatings deposited from the electrodepositable coating composition.

[0195] Non-limiting examples of hybrid organic-inorganic materials include organohalogen compounds, phosphorus-containing resins such as organophosphorus compounds, silicone resins, sulfur-containing resins, nanogels, or combinations thereof.

[0196] Suitable examples of organic halogen compounds include organic chlorine compounds (e.g., chlorendic acid derivatives and chlorinated paraffins), organic bromine compounds (e.g., decabromodiphenyl ether (decaBDE) and decabromodiphenylethane (a substitute for decaBDE)), polymeric bromine compounds (e.g., brominated polystyrene, brominated carbonate oligomer (BCO), brominated epoxy oligomer (BEO), tetrabromophthalic anhydride), tetrabromobisphenol A (TBBPA), and hexabromocyclododecane (HBCD). These halogenated materials may be used in combination with a synergist to enhance their efficiency. Other suitable examples include antimony trioxide, antimony pentoxide, and sodium antimonate.

[0197] Suitable examples of organophosphorus compounds include triphenyl phosphate (TPP), resorcinol bis(diphenyl phosphate) (RDP), bisphenol A diphenyl phosphate (BADP), and tricresyl phosphate (TCP), as well as phosphonates such as dimethyl methyl phosphonate (DMMP) and phosphinates such as aluminum diethyl phosphinate.

[0198] Hybrid organic-inorganic materials may also include compounds containing both phosphorus and halogens, such as tris(2,3-dibromopropyl)phosphate (brominated tris), tris(1,3-dichloro-2-propyl)phosphate (chlorinated tris or TDCPP), and chlorinated organophosphates such as tetrakis(2-chloroethyl)dichloroisopentyl diphosphate (V6).

[0199] The hybrid organic-inorganic material may also include ammonium polyphosphate.

[0200] The electrodeposition coating and / or electrodepositable coating composition may optionally further comprise an organic flame retardant additive.

[0201] As used herein, the term "organic flame retardant additive" refers to an organic compound that contributes to the flame retardancy of a coating, where the "organic" in "organic flame retardant additive" refers to a material that contains carbon and, optionally, further contains hydrogen, oxygen, and / or nitrogen atoms. For clarity, "organic flame retardant additive" includes melamine and melamine derivatives, even if the melamine derivatives contain atoms other than carbon, hydrogen, oxygen, and nitrogen.

[0202] The organic flame retardant additive may include organic compounds such as carboxylic acids, dicarboxylic acids, melamine and its derivatives (including those containing phosphates), phenoplast resins, organic nitrogen compounds, etc. For example, the organic compound may include carboxylic acids, dicarboxylic acids, melamine, melamine polyphosphate, melamine poly(zinc) phosphate, melamine poly(aluminum) phosphate, melamine-based hindered amine light stabilizers, phenoplast resins, expandable graphite, organic nitrogen compounds, or combinations thereof.

[0203] The electrodeposition coating and / or electrodepositable coating composition may be substantially free, substantially free, or completely free of montmorillonite.

[0204] According to the present disclosure, the electrodepositable coating composition may contain water and / or one or more organic solvent(s). Water may be present, for example, in an amount of 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, such as monoalkyl ethers (having 1 to 10 carbon atoms in the alkyl group) of ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol, such as the monoethyl and monobutyl ethers of these glycols. Examples of other at least partially water-miscible solvents include alcohols, such as ethanol, isopropanol, butanol, and diacetone alcohol. When an organic solvent is used, it 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, particularly an aqueous dispersion.

[0205] According to the present disclosure, the total solids content of the electrodepositable coating composition may be at least 1 wt %, such as at least 5 wt %, and may be 50 wt % or less, such as 40 wt % or less, such as 20 wt % or less, based on the total weight of the electrodepositable coating composition. The total solids content of the electrodepositable coating composition may be 1 wt % to 50 wt %, such as 5 wt % to 40 wt %, such as 5 wt % to 20 wt %, based on the total weight of the electrodepositable coating composition. As used herein, "total solids" refers to the non-volatile content of the electrodepositable coating composition, i.e., materials that do not volatilize when heated at 110°C for 15 minutes.

[0206] Base material According to the present disclosure, the electrodepositable coating composition can be electrophoretically applied to a conductive substrate. The electrodepositable coating composition can be electrophoretically applied to any conductive substrate. Suitable substrates include metal substrates, metal alloy substrates, and / or metallized substrates, such as nickel-plated plastics. In addition, substrates can include non-metallic conductive materials, including composite materials such as carbon fiber or conductive carbon-containing materials. According to the present disclosure, metals or metal alloys can include cold-rolled steel, hot-rolled steel, stainless steel, zinc metal-coated steel, zinc compounds, or zinc alloys, such as electrogalvanized steel, hot-dip galvanized steel, galvanized steel, and zinc alloy-plated steel. Aluminum alloys of the 2XXX, 3XXX, 4XXX, 5XXX, 6XXX, or 7XXX series, as well as clad and cast aluminum alloys of the A356 series, can also be used as substrates. Magnesium alloys of the AZ31B, AZ91C, AM60B, or EV31A series can also be used as substrates. Substrates used in the present disclosure can also include titanium and / or titanium alloys. Other suitable non-ferrous metals include copper and magnesium, as well as alloys of these materials. Metal substrates suitable for use in the present disclosure include those commonly used in the assembly of industrial structures and components, such as vehicle bodies (e.g., but not limited to, doors, body panels, trunk deck lids, roof panels, hoods, roofs and / or stringers, rivets, landing gear components, and / or skin panels used in aircraft), vehicle frames, vehicle parts, motorcycles, wheels, appliances including washers, dryers, refrigerators, stoves, dishwashers, etc., agricultural equipment, lawn and garden equipment, air conditioning units, heat pump units, lawn furniture, and other items. As used herein, "vehicle" or variations thereof include, but are not limited to, civilian aircraft, commercial aircraft, military aircraft, and / or land vehicles such as automobiles, motorcycles, trucks, tanks, and / or armored vehicles and trucks. Metal substrates may also be in the form of, for example, metal sheets or fabricated parts.It will also be appreciated that the substrate may be pretreated with a pretreatment solution, such as a zinc phosphate pretreatment solution as described, for example, in U.S. Pat. Nos. 4,793,867 and 5,588,989, or a zirconium-containing pretreatment solution as described, for example, in U.S. Pat. Nos. 7,749,368 and 8,673,091.

[0207] The substrate may be a composite metal body. As used herein, the term "composite metal body" refers to (1) an article having at least one surface composed of a first metal and at least one surface composed of a second metal different from the first metal, (2) a first article having at least one surface composed of a first metal and a second article having at least one surface composed of a second metal different from the first metal, or (3) both (1) and (2). The substrate may be composed of adjacent or joined surfaces or portions of different substrate materials, such as in a galvanic assembly.

[0208] Coating method, coating, and coated substrate The electrodepositable coating composition may be electrophoretically applied to an electrically conductive substrate and at least partially cured using application conditions, times, and temperatures known to those skilled in the art.

[0209] The cationic electrodepositable coating compositions of the present disclosure can be deposited onto a conductive substrate by contacting the composition with a conductive cathode and a conductive anode, the surface to be coated being the cathode. After contact with the composition, when a sufficient voltage is applied between the electrodes, an adherent film of the coating composition can be deposited on the cathode.

[0210] The anionic electrodepositable coating compositions of the present disclosure can be deposited onto a conductive substrate by contacting the composition with a conductive cathode and a conductive anode, the surface to be coated being the anode. After contact with the composition, when a sufficient voltage is applied between the electrodes, an adherent film of the coating composition can be deposited on the anode.

[0211] The applied voltage in the electrophoretic application of the electrodepositable coating compositions of the present disclosure may vary and can be as low as 1 volt to as high as several thousand volts, for example, between 50 and 500 volts. The current density, for example, between 0.5 and 15 amps per square foot, tends to decrease during electrodeposition, indicating the formation of an insulating film.

[0212] A substrate at least partially coated with an electrodepositable coating layer deposited from a coating composition of the present disclosure may be heated to a temperature and for a time sufficient to at least partially cure the electrodeposited coating on the substrate. As used herein, the term "at least partially cure" refers to subjecting the coating composition to curing conditions such that at least a portion of the reactive groups on the components of the coating composition cure or crosslink to form a coating. Generally, the substrate may be heated to a temperature in the range of 250°F to 450°F (121.1°C to 232.2°C), such as 275°F to 400°F (135°C to 204.4°C), e.g., 300°F to 360°F (149°C to 180°C). For purposes of the present disclosure, all that is required is that the time be sufficient to achieve cure of the coating on the substrate. The curing time may range, for example, from 10 minutes to 60 minutes, e.g., from 20 minutes to 40 minutes. The thickness of the electrodeposition coating obtained after curing is not particularly limited, and may be optionally set within the range of 15 to 50 microns.

[0213] The present disclosure also relates to a method of coating a substrate, such as any one of the aforementioned conductive substrates. According to the present disclosure, such a method may include electrophoretically applying an electrodepositable coating composition to at least a portion of the substrate, as described above, and curing the coating composition to form an at least partially cured coating on the substrate. According to the present disclosure, the method may include (a) electrophoretically depositing an electrodepositable coating composition of the present disclosure onto at least a portion of the substrate, and (b) heating the coated substrate to a temperature and for a time sufficient to cure the electrodeposited coating on the substrate. According to the present disclosure, the method may optionally further include (c) applying one or more pigmented coating compositions and / or one or more non-pigmented coating compositions directly to the at least partially cured electrodeposited coating to form a topcoat covering at least a portion of the at least partially cured electrodeposited coating, and (d) heating the coated substrate of step (c) to a temperature and for a time sufficient to cure the topcoat.

[0214] The electrodepositable coating composition of the present disclosure may comprise a multi-layer coating system. A coating layer deposited from the present composition may have one or more additional coating layers deposited thereon and / or thereon. In a non-limiting example, the coating system may include a pretreatment layer, such as a phosphate layer (e.g., a zinc phosphate layer), and the electrodepositable coating composition described herein may be deposited on at least a portion of the pretreatment layer. One or more additional coating layers may be applied on at least a portion of the electrodeposited coating layer. In addition to the electrodepositable coating composition of the present disclosure, the coating system may include, for example, one or more pretreatment layers and one or more additional coating layers, including a primer, basecoat, colorcoat, monocoat, clearcoat, and / or topcoat. Suitable additional coating layers include those known in the art and may each independently be in the form of an aqueous, solvent-borne, solid particulate (i.e., powder coating composition), or powder slurry. The additional coating layers may be cured independently or, optionally, applied "wet-on-wet" and cured simultaneously. As used herein, "wet-on-wet" refers to the process of applying a coating, such as a clearcoat, over another coating, such as a colorcoat, that is still largely uncured, and curing both coatings simultaneously.

[0215] The coating system may optionally contain one or more mixtures of colorants and / or fillers in any amount sufficient to impart the desired properties, visual and / or color effect in any coating layer or layers, as is well known to those skilled in the art.

[0216] The present disclosure further relates to electrodepositable coatings formed by at least partially curing a film from the electrodepositable coating composition described herein.

[0217] The present disclosure also relates to coated substrates comprising a coating deposited from the above-described electrodepositable coating composition.

[0218] The coated substrate may be coated by the methods described herein.

[0219] The coated conductive substrate may optionally not include a pretreatment layer between the substrate and the electrodeposition coating, or there may be no pretreatment layer present.

[0220] The coated conductive substrate may optionally not include an intervening coating layer between the substrate and the electrodeposition coating.

[0221] Additionally, the topcoat layer may be applied directly onto the electrodepositable coating layer. In other words, the substrate may be free of a primer layer. For example, a basecoat layer may be applied directly onto at least a portion of the electrodepositable coating layer.

[0222] Electrodeposition coating is 55g / m per day 2 It may have a water vapor transmission rate (as measured by the WATER VAPOR TRANSMITTANCE TEST METHOD) of less than 50 g / m per day, for example 2 Less than, say, 45 g / m per day 2 Less than, for example, 40 g / m per day 2 It may have less than

[0223] The electrodeposition coating may have an edge coverage of greater than 20% (as measured by the EDGE COVERAGE TEST METHOD), such as greater than 30%, such as greater than 40%, such as greater than 50%, such as greater than 60%, such as greater than 70%, such as greater than 80%, such as greater than 90%, such as greater than 95%.

[0224] As used herein, unless otherwise defined, the term "substantially free" means that the component is present in an amount of 1% by weight or less, based on the total weight of the electrodepositable coating and / or the total solids weight of the electrodepositable coating composition.

[0225] As used herein, unless otherwise defined, the term "substantially free" means that the component is present in an amount of 0.1 wt. % or less, based on the total weight of the electrodepositable coating and / or the total solids weight of the electrodepositable coating composition.

[0226] As used herein, unless otherwise defined, the term "completely free" means that the component is not present in the coating composition, i.e., 0.00 wt. % based on the total weight of the electrodepositable coating and / or the total solids weight of the electrodepositable coating composition.

[0227] For purposes of this detailed description, it should be understood that the present disclosure may contemplate alternative variations and step sequences unless expressly specified to the contrary. Further, other than in any examples or unless otherwise indicated, all numerical values ​​expressing quantities of components used in the specification and claims, for example, should be understood as being modified in all instances by the term "about." Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and appended claims are approximations that may vary depending upon the desired properties to be obtained by the present disclosure. At the very least, the application of the doctrine of equivalents is not intended to limit the scope of the claims, and each numerical parameter should be construed in light of at least the number of reported significant digits and by applying ordinary rounding techniques.

[0228] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values ​​set forth in the specific examples are reported as precisely as possible. However, any numerical value inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0229] It should also be understood that any numerical range recited herein is intended to include all subranges subsumed therein. For example, a range of "1 to 10" is intended to include all subranges between (and including) the recited minimum of 1 and the recited maximum of 10, i.e., minimums of 1 or greater and maximums of 10 or less.

[0230] As used herein, "including," "containing," and similar terms are understood to be synonymous with "comprising" in the context of this application and, therefore, are open-ended and do not exclude the presence of additional, undescribed or unlisted elements, materials, components, or method steps. As used herein, "consisting of" is understood in the context of this application to exclude the presence of any unspecified element, component, or method step. As used herein, "consisting essentially of" is understood in the context of this application to include specified elements, materials, components, or method steps, and those that are described "that do not materially affect the basic and novel characteristics."

[0231] In this application, unless otherwise specified, the use of the singular includes the plural, and the plural encompasses the singular. For example, although this specification refers to "one" ionizable salt group-containing film-forming polymer, "one" hydroxyl-functional addition polymer, "one" monomer, "one" ionizable salt group-containing film-forming polymer, and "one" blocked polyisocyanate curing agent, combinations (i.e., multiples) of these components may be used. Additionally, in this application, the use of "or" means "and / or" unless otherwise specified, even though "and / or" may be explicitly used in certain instances.

[0232] While particular aspects of the present disclosure have been described in detail, it will be understood by those skilled in the art that various modifications and alternatives to those details may be developed in light of the overall teachings of the present disclosure. Accordingly, the particular configurations disclosed are meant to be illustrative only, and not limiting, of the scope of the present disclosure, which is given the full scope of the appended claims and any and all equivalents thereof.

[0233] The following examples illustrate the present disclosure but should not be construed as limiting the disclosure to the details thereof. Unless otherwise indicated, all parts and percentages in the following examples, as well as throughout the specification, are by weight. [Example]

[0234] Preparation of Resin Systems for Examples 1-9 Preparation of Crosslinker I. A blocked polyisocyanate crosslinker suitable for use in electrodepositable coating resins was prepared in the following manner. Components 2 through 6, listed in Table 1 below, were mixed in a flask set at full reflux under nitrogen with stirring. The mixture was heated to a temperature of 110°C, and component 1 was added dropwise, allowing the temperature to rise due to the exotherm of reaction and remain below 110°C. After the addition of component 1 was complete, component 7 was added to the heated reaction mixture. The temperature was set to 110°C in the reaction mixture, and the reaction mixture was held at that temperature until no residual isocyanate was detected by IR spectroscopy. Components 8 and 9 were then added, and the reaction mixture was stirred for 30 minutes and cooled to ambient temperature. [Table 1]

[0235] Preparation of Cationic, Amine-Functionalized, Polyepoxide-Based Resin (Resin System I): A cationic, amine-functionalized, polyepoxide-based polymeric resin suitable for use in formulating electrodepositable coating compositions was prepared by the following method. Components 1 through 4, listed in Table 2 below, were combined in a flask set to total reflux under nitrogen with stirring. The mixture was heated to a temperature of 130°C and allowed to exotherm (maximum 170°C). The temperature in the reaction mixture was set to 145°C, and the reaction mixture was held for 1.5 hours. Components 5 through 7 were then introduced into the reaction mixture, and the temperature in the reaction mixture was set to 100°C. Components 8 and 9 were then quickly added to the reaction mixture, and the reaction mixture was allowed to exotherm. The temperature in the reaction mixture was set to 110°C, and the reaction mixture was held for 1 hour. After the hold, the heat source was removed from the reaction mixture, and component 10 was slowly introduced. The contents of the flask were stirred while cooling to room temperature. The resulting Resin Synthesis Product I had a solids content of 86.9% by weight. [Table 2]

[0236] Preparation of Crosslinker II. A blocked polyisocyanate crosslinker suitable for use in electrodepositable coating compositions was prepared in the following manner. Components 2-4, shown in Table 3 below, were mixed in a flask set at total reflux with stirring under nitrogen. Component 1 was added to the mixture over 1 hour under nitrogen, maintaining the temperature below 100°C. After the addition of component 1 was complete, the flask was rinsed with component 5 and held at 100°C for 1 hour. Components 6 and 7 were then added to the flask, and the mixture was mixed for 30 minutes and cooled to ambient temperature. [Table 3]

[0237] Preparation of Cationic, Amine-Functionalized, Polyepoxide-Based Resin (Resin System II): A cationic, amine-functionalized, polyepoxide-based polymeric resin suitable for use in formulating electrodepositable coating compositions was prepared by the following method. Components 1-4, shown in Table 4 below, were combined in a flask set to total reflux under nitrogen with stirring. The mixture was heated to a temperature of 130°C and allowed to exotherm (maximum 170°C). The temperature in the reaction mixture was set to 145°C, and the reaction mixture was held for 1.5 hours. Component 5 was then introduced into the reaction mixture, and the temperature in the reaction mixture was set to 100°C and mixed for 10 minutes. Components 6 and 7 were then introduced into the reaction mixture and mixed for 10 minutes. Components 8 and 9 were then quickly added to the reaction mixture, and the reaction mixture was allowed to exotherm. The temperature in the reaction mixture was set to 110°C, and the reaction mixture was held for 1 hour. After the hold, the heat source was removed from the reaction mixture, and component 10 was slowly introduced. The contents of the flask were stirred for at least 15 minutes while cooling to room temperature. The resulting resin synthesis product II had a solids content of 86.2% by weight. [Table 4]

[0238] Preparation of Cationic, Amine-Functionalized, Polyepoxide-Based Resin (Resin System III) A cationic, amine-functionalized, polyepoxide-based polymeric resin suitable for use in formulating electrodepositable coating compositions was prepared by the following method. Components 1-3, listed in Table 5 below, were combined in a flask set to total reflux under nitrogen with stirring. The mixture was heated to a temperature of 130°C and mixed. Component 4 was added to the mixture, the temperature was set to 135°C, and held for at least one hour until the target epoxy equivalent weight of 549 was achieved. Component 5 was then added to the mixture, and the temperature of the reaction mixture was set to 100°C. Components 6 and 7 were then added to the reaction mixture, and allowed to exotherm. The temperature of the reaction mixture was set to 95°C, and the mixture was stirred for three hours. The contents of the flask were then dissolved in a pre-blended mixture of Components 8 and 9 and mixed for 30 minutes. Component 10 was then added over 30 minutes. The resulting Resin Synthesis Product III had a solids content of 45% by weight. [Table 5]

[0239] Preparation of Cationic, Amine-Functionalized, Polyepoxide-Based Resin (Resin System IV) A cationic, amine-functionalized, polyepoxide-based polymeric resin, suitable for use in formulating electrodepositable coating compositions, was prepared by the following method. Components 1-4, shown in Table 6 below, were combined in a flask set to total reflux under nitrogen with stirring. The mixture was heated to a temperature of 130°C and allowed to exotherm (maximum 170°C). The temperature in the reaction mixture was set to 145°C, and the reaction mixture was held for 1.5 hours. Component 5 was then introduced into the reaction mixture, and the temperature in the reaction mixture was set to 100°C and mixed for 10 minutes. Component 7 was then introduced into the reaction mixture and mixed for 10 minutes. Components 7 and 8 were then quickly added to the reaction mixture, and the reaction mixture was allowed to exotherm. The temperature in the reaction mixture was set to 110°C, and the reaction mixture was held for 1 hour. After the hold, the heat source was removed from the reaction mixture, and component 9 was slowly introduced. The contents of the flask were stirred for at least 15 minutes while cooling to room temperature. The resulting resin synthesis product II had a solids content of 86.2% by weight. [Table 6]

[0240] Preparation of Electrodepositable Coating Compositions of Examples 1-5 Formulation Additives and Chemical Sources. Chemicals used in the preparation of the electrodeposition baths were obtained from various sources. Butyl carbitol formal was commercially available from BASF as MAZON 1651 (98% purity). Ethylene glycol monobutyl ether (butyl cellosolve) was commercially available from MILLIPORESIGMA / SIGMA-ALDRICH CORPORATION. Dowanol PM was obtained from The Dow Chemical Company at 98% purity. Triethylene glycol monomethyl ether (TGME) was obtained from Sigma-Aldrich Corporation at 98% purity. Sulfamic acid and phosphoric acid (85 wt.% active concentration in water) were obtained from PPG Industries, Inc.

[0241] Example 1: A highly pigmented electrodepositable coating composition was prepared in the following manner. Components 1-3 listed in Table 7 below were placed in a stainless steel beaker and mixed at high shear (2500 RPM using a 1.5-inch Cowles blade powered by a Fawcett Air Motor Model 103A) for 5 minutes at 40°C. The temperature was raised to above 60°C, and the mixture was held at the above mixing conditions for 1 hour, after which the degree of dispersion was measured with a Hegman gauge. A minimum reading of 5 was required for proper dispersion.

[0242] In the dispersion step, a mixture of components 4-6 was added to the clay / resin I paste. The temperature was set to less than 60°C, and the dispersion was mixed with a high-lift blade at 1500 RPM for 1 hour. After dispersion, the dispersion was cooled to ambient temperature, and component 7 was added to bring the final solids content of the dispersion paste to 50% by weight. Component 8 was then added to the dispersion formulation, and the mixture was mixed at ambient temperature for 1 hour to complete the high-solids feed solution. To produce the electrodeposition bath composition, the high-solids feed solution was further diluted with component 9 to a solids content of 25% by weight. [Table 7]

[0243] Example 2: A highly pigmented electrodepositable coating composition was prepared in the following manner. Components 1-3 listed in Table 8 below were placed in a stainless steel beaker and mixed at high shear (2500 RPM using a 1.5-inch Cowles blade powered by a Fawcett Air Motor Model 103A) for 5 minutes at 40°C. The temperature was raised to above 60°C, and the mixture was held at the above mixing conditions for 1 hour, after which the degree of dispersion was measured with a Hegman gauge. A minimum reading of 5 was required for proper dispersion.

[0244] In the dispersion step, a mixture of components 4-6 was added to the clay / resin I paste. The temperature was set to less than 60°C, and the dispersion was mixed for 1 hour with a high-lift blade at 1500 RPM. After dispersion, the dispersion was cooled to ambient temperature, and component 7 was added to achieve a final solids content of 50% by weight of the dispersion paste. Component 8 was then added to the dispersion formulation and mixed for 1 hour at ambient temperature to complete the high-solids feed solution. The high-solids feed solution was further diluted with component 9 to a solids content of 25% by weight. To produce the electrodeposition bath composition, the electrodeposition bath was heated to 95°F, and component 10 was added. The electrodeposition bath composition was mixed for 2 hours before repeating the test after addition. [Table 8]

[0245] Comparative Examples 3-5: Examples 2-4 were prepared according to the following general procedure. Ingredients 1-3 shown in Table 9 below were placed in a stainless steel beaker and mixed at 40°C for 5 minutes at high shear (2500 RPM using a 1.5-inch Cowles blade powered by a Fawcett Air Motor Model 103A). The temperature was raised to above 60°C, and the mixture was held at the above mixing conditions for 1 hour, after which the degree of dispersion was measured with a Hegman gauge. A minimum reading of 5 was required for proper dispersion.

[0246] In the dispersion step, a mixture of components 4-6 was added to the clay / resin I paste. The temperature was set to less than 60°C, and the dispersion was mixed with a high-lift blade at 1500 RPM for 1 hour. After dispersion, the dispersion was cooled to ambient temperature, and component 7 was added. Component 8 was then added to the dispersion and mixed at ambient temperature for 1 hour to complete the high-solids feed solution. To produce the electrodeposition bath composition, the high-solids feed solution was further diluted with component 9 to a solids content of 25% by weight, except for Example 4, which was diluted with component 9 to a solids content of 15%. [Table 9]

[0247] Evaluation test methods for Examples 1 to 5 Edge Burr Coverage Evaluation: Zinc phosphate-pretreated CRS panels (C700 / DI, product number 28630, available from ACT, Inc., Hillsdale, Michigan) were cut in half to yield 4-inch by 6-inch panels. 0.25 inches was then removed from one edge of the panel, resulting in 3.75-inch by 6-inch panels with burred edges on both sides. These burred edges were used to test the ability of the electrocoat coating to cover sharp edges. The panels were immersed in the electrocoat coating and electrocoated using a rectifier (Xantrax, Model XFR600-2, Elkhart, Indiana, or Sorensen, Model XZG 300-5.6, Ametek, Berwyn, Pennsylvania) powering a DC source. The target coating thickness was 1.0 mil (25.4 microns) on the vertical surface of the panel. The exact application conditions for each coating are listed in Table 10. After the panels were electrocoated, they were rinsed with deionized water and baked in an electric oven (Despatch Model LFD-1-42) at 177°C for 30 minutes.

[0248] Three panels coated with each electrodeposition coating composition were placed in the ASTM-B117 Neutral Salt Spray Corrosion Test with the burred edge facing up for a total of 7 days (168 hours). After testing, the panels were rinsed with isopropyl alcohol to remove residual moisture and air-dried. The amount of corrosion along the burred edge was then measured and reported in Table 11. Corrosion was quantified by manually measuring the total length of the burred edge that was free of red rust and protected from corrosion. The percentage of the edge that was covered was calculated by dividing the uncorroded length by the total length of the burred edge. This test method is referred to herein as the Edge Coverage Test Method.

[0249] Elongation Flexibility Evaluation: Zinc phosphate-pretreated CRS panels (C700 / DI, product number 28630, available from ACT, Hillsdale, Michigan) were cut in half to yield 4" x 6" panels. These panels were immersed in the electrocoat paint and electrocoated using a rectifier (Xantrax, Model XFR600-2, Elkhart, Indiana, or Ametek, Sorensen, Model XZG 300-5.6, Berwyn, Pennsylvania) powered by a DC power source. The target film thickness was 1.0 mil (25.4 microns) on the vertical surface of the panel. The exact coating conditions for each paint are listed in Table 10. After electrocoating, the panels were rinsed with deionized water and baked in an electric oven (Despatch Model LFD-1-42) at 177°C for 30 minutes.

[0250] Two panels coated with each electrodeposition coating composition were subjected to the mandrel bend elongation flexibility test according to ASTM D522. The panels were placed vertically in the fixture, locked in place, and bent along the fixture's conical support. Tape was repeatedly applied and removed from the bent area to remove weakly adherent coatings, until the coating no longer adhered to the tape. The peeled area from the edge of the bent area to the point where the coating no longer peeled was measured with a ruler. The amount of peeling along the conical bend is shown in Table 11.

[0251] Evaluation of the glass transition temperature of the coating film: To determine the glass transition temperature, a free film of the exemplified electrodeposition paint was first produced using a conductive electrodeposition paint. The formulation and method of use of the conductive electrodeposition paint are described in detail below.

[0252] A conductive electrodeposition paint was prepared using PPG products commercially available under product codes CR756 and CP639. Deionized water (1959 g) was added to 2093 g of CR756 and 220 g of CP639 paste under stirring for 1 hour. This material was used to electrodeposit the panels according to the specifications in the technical bulletin.

[0253] CRS panels (C700 / DI, product number 28630, available from ACT, Hillsdale, Michigan) pretreated with zinc phosphate were cut in half to yield 4" x 6" panels. These panels were immersed in conductive electrocoat paint and electrocoated using a rectifier (Xantrax, Elkhart, Indiana, Model XFR600-2, or Ametek, Berwyn, Pennsylvania, Model Sorensen XZG 300-5.6) powered by a DC power source. The target thickness was 0.5 to 0.7 mil (12.7 to 17.8 micrometers) on the vertical surface of the panel. To achieve the target thickness per panel, the electrocoat bath was maintained at 80°F, used 115 volts, and limited to 0.75 amps. Coating was continued until 40 coulombs were produced. After the panels were electrocoated, they were rinsed with deionized water and baked in an electric oven (Despatch Model LFD-1-42) at 219°C for 90 minutes.

[0254] The conductive electrodeposition paint-coated panels were then immersed in the example electrodeposition paint and electrodeposited using a DC powered rectifier (Xantrax Model XFR600-2, Elkhart, Indiana, or Ametek Sorensen Model XZG 300-5.6, Berwyn, Pennsylvania). The target film thickness was 1.0 mil (25.4 microns) on the vertical surface of the panel. The exact coating conditions for each paint are listed in Table 10. After electrodeposition coating, the panels were rinsed with deionized water and baked in an electric oven (Despatch Model LFD-1-42) at 177°C for 30 minutes. The example electrodeposition paint was then removed from the conductive electrodeposition panel and used to measure the glass transition temperature.

[0255] Glass transition temperature (T g ) was measured using a dynamic mechanical analyzer (DMA). A TA Instruments Discovery DMA 850 instrument was used in tension mode, with a preload of 10 mN, an amplitude of 15 μm (tensile strain <0.3%), a static / dynamic stress amplitude ratio (so-called "force tracking") of 125%, and an oscillation frequency of 1 Hz. Samples were first cut into rectangles measuring 7 mm wide, 15 mm long, and 25 μm thick. Each film specimen was subjected to tensile stress at room temperature, then cooled to -125°C for thermal equilibration, and heated to 200°C at a rate of 3°C / min. T g was determined by the peak temperature value of the loss tangent (tanδ). g is shown in Table 11.

[0256] Evaluation of Cured Coating Structure: Zinc phosphate-pretreated CRS panels (C700 / DI, product number 28630, available from ACT, Hillsdale, Michigan) were cut in half to yield 4" x 6" panels. These panels were immersed in the electrocoat paint and electrocoated using a DC powered rectifier (Xantrax, Model XFR600-2, Elkhart, Indiana, or Ametek, Sorensen, Model XZG 300-5.6, Berwyn, Pennsylvania). The target coating thickness was 1.0 mil (25.4 microns) on the vertical surface of the panel. The exact coating conditions for each paint are listed in Table 10. After electrocoating, the panels were rinsed with deionized water and baked in an electric oven (Despatch Model LFD-1-42) at 177°C for 30 minutes.

[0257] The panels were then prepared for TEM analysis. They were cut to size, embedded in EMBed-812 epoxy resin, and cured at 60°C for 24 hours. They were then sectioned with an ultrathin microtome to obtain thin sections (<80 nm) that were collected on copper TEM grids. Bright-field images were acquired with a Tecnai T20 TEM operating at 200 kV, and the images for Examples 1-5 are shown in Figure 1. The maximum Feret diameter of the sparse domains was determined by measuring 10 domains in three different images using ImageJ. The measured domain sizes are shown in Table 11.

[0258] Evaluation of Examples 1 to 5 As shown in Tables 10 and 11, electrocoatings containing platelet pigments with a pigment to binder ratio of at least 0.4:1 exhibited multiple T g These results indicate the formation of resin domains with improved edge corrosion resistance and elongation flexibility. Furthermore, the size of these domains can be adjusted to modify these properties. [Table 10] [Table 11]

[0259] Preparation of Electrodepositable Coating Compositions of Examples 6-9 Comparative Examples 6 and 7: Highly pigmented electrodepositable coating compositions were prepared in the following manner. Components 1-4 listed in Table 12 below were placed in a stainless steel beaker and mixed at high shear (2500 RPM using a 1.5-inch Cowles blade powered by a Fawcett Air Motor Model 103A) for 5 minutes at 40°C. The temperature was raised to above 60°C, and the mixture was held at the above mixing conditions for 1 hour, after which the degree of dispersion was measured with a Hegman gauge. A minimum reading of 5 was required for proper dispersion.

[0260] In the dispersion step, a mixture of components 5 and 6 was added to the clay / resin II paste. The temperature was set to less than 60°C, and the dispersion was mixed for one hour with a high-lift blade at 1500 RPM. After dispersion, the dispersion was cooled to ambient temperature, and components 7 and 8 were added and mixed for one hour to bring the final solids content of the dispersion paste to 40% by weight. Component 9 was then added to the dispersion formulation and mixed for one hour at ambient temperature to complete the high solids feed. To produce the electrodeposition bath composition, the high solids feed was further diluted with component 10 to a solids content of 25% by weight. [Table 12]

[0261] Comparative Example 8: A highly pigmented electrodepositable coating composition was prepared in the following manner. Components 1-4 listed in Table 13 below were placed in a stainless steel beaker and mixed at high shear (2500 RPM using a 1.5-inch Cowles blade powered by a Fawcett Air Motor Model 103A) for 5 minutes at 40°C. The temperature was raised to above 60°C, and the mixture was held at the above mixing conditions for 1 hour, after which the degree of dispersion was measured with a Hegman gauge. A minimum reading of 5 was required for proper dispersion.

[0262] In the dispersion step, a mixture of components 5 and 6 was added to the clay / resin II / resin IV paste. The temperature was set to less than 60°C and the dispersion was mixed with a high-lift blade at 1500 RPM for one hour. The final solids content of this dispersion paste was 30% by weight. Component 7 was then added to the dispersion formulation and mixed for one hour at ambient temperature to complete the high solids feed. To produce the electrodeposition bath composition, the high solids feed was further diluted with component 8 to a solids content of 25% by weight. [Table 13]

[0263] Comparative Example 9: A highly pigmented electrodepositable coating composition was prepared in the following manner. Components 1-3 listed in Table 14 below were placed in a stainless steel beaker and mixed at high shear (2500 RPM using a 1.5-inch Cowles blade powered by a Fawcett Air Motor Model 103A) for 5 minutes at 40°C. The temperature was raised to above 60°C, and the mixture was held at the above mixing conditions for 1 hour, after which the degree of dispersion was measured with a Hegman gauge. A minimum reading of 5 was required for proper dispersion.

[0264] In the dispersion step, a mixture of components 4 and 5 was added to the clay / resin II paste. The temperature was set to less than 60°C, and the dispersion was mixed with a high-lift blade at 1500 RPM for one hour. After dispersion, the dispersion was cooled to ambient temperature, and component 6 was added and mixed for one hour to achieve a final solids content of 30% by weight of the dispersion paste. Component 7 was then added to the dispersion formulation and mixed for one hour at ambient temperature to complete the high solids feed. To produce the electrodeposition bath composition, the high solids feed was further diluted with component 8 to a solids content of 25% by weight. [Table 14]

[0265] Evaluation test methods for Examples 6 to 9 Evaluation of elongation flexibility: The same tests as those carried out to evaluate elongation flexibility in Examples 1-5 were also carried out in Examples 6-9.

[0266] Evaluation of Cured Coating Structure: The same tests performed to evaluate resin domain formation in the cured coating structure for Examples 1-5 were also performed for Examples 6-9, except for Examples 6-9, where domain formation was reported as either present in the coating structure or absent in the coating structure.

[0267] Evaluation of water vapor permeability of coating film: To obtain the water vapor permeability, first, a free film of the electrodeposition paint of Examples 6 to 9 was produced using a conductive electrodeposition paint. The formulation and method of use of the conductive electrodeposition paint are described in detail below.

[0268] A conductive electrodeposition paint was prepared using PPG products commercially available under product codes CR756 and CP639. Deionized water (1959 g) was added to 2093 g of CR756 and 220 g of CP639 paste under stirring for 1 hour. This material was used to electrodeposit the panels according to the specifications in the technical bulletin.

[0269] CRS panels (C700 / DI, product number 28630, available from ACT, Hillsdale, Michigan) pretreated with zinc phosphate were cut in half to yield 4" x 6" panels. These panels were immersed in conductive electrocoat paint and electrocoated using a rectifier (Xantrax, Elkhart, Indiana, Model XFR600-2, or Ametek, Berwyn, Pennsylvania, Model Sorensen XZG 300-5.6) powered by a DC power source. The target thickness was 0.5 to 0.7 mil (12.7 to 17.8 micrometers) on the vertical surface of the panel. To achieve the target thickness per panel, the electrocoat bath was maintained at 80°F, used 115 volts, and limited to 0.75 amps. Coating was continued until 40 coulombs were produced. After the panels were electrocoated, they were rinsed with deionized water and baked in an electric oven (Despatch Model LFD-1-42) at 219°C for 90 minutes.

[0270] The conductive electrodeposition paint-coated panels were then immersed in the example electrodeposition paint and electrodeposited using a DC powered rectifier (Xantrax Model XFR600-2, Elkhart, Indiana, or Ametek Sorensen Model XZG 300-5.6, Berwyn, Pennsylvania). The target film thickness was 1.0 mil (25.4 microns) on the vertical surface of the panel. The exact coating conditions for each paint are listed in Table 15. After electrodeposition coating, the panels were rinsed with deionized water and baked in an electric oven (Despatch Model LFD-1-42) at 177°C for 30 minutes. The example electrodeposition paint was then removed from the conductive electrodeposition panel and used to measure the glass transition temperature.

[0271] Water vapor transmission rates were measured according to ASTM F-1249 using a Permatran-W 3 / 34 WVTR analyzer. Each sample was masked between two pieces of self-adhesive aluminum foil. The test area was 5.00 cm. 2 The samples were tested at 37.8°C and 90% room humidity. This test method is referred to herein as the WATER VAPOR TRANSMITTANCE TEST METHOD. The measured transmittance values ​​for Examples 6-9 are shown in Table 16.

[0272] Evaluation of Examples 6 to 9 The results shown in Table 16 demonstrate that the use of platelet pigments in combination with domains in the coating structure provides a balanced improvement in reduced water vapor permeability and increased elongational flexibility of the coating. [Table 15] [Table 16]

[0273] It will be appreciated by those skilled in the art that numerous modifications and variations are possible in light of the foregoing disclosure without departing from the broad inventive concept described and illustrated herein. It should therefore be understood that the foregoing disclosure is merely illustrative of various exemplary aspects of the present application, and that numerous modifications and variations may be readily made by those skilled in the art that are within the spirit and scope of the present application and the appended claims.

Claims

1. 1. A coated conductive substrate comprising an electrodeposited coating deposited from an electrodepositable coating composition, said electrodeposited coating comprising: a platelet-like pigment present in a pigment to binder ratio of at least 0.4:1; an electrodeposited binder, wherein the electrodeposited binder comprises: a first resin domain having a first glass transition temperature; a second resin domain having a second glass transition temperature, wherein said first glass transition temperature is at least 10°C higher than said second glass transition temperature, such as at least 20°C, for example at least 30°C, such as at least 40°C, for example at least 50°C, such as at least 60°C, for example at least 70°C, such as at least 80°C, for example at least 90°C, such as at least 100°C, for example at least 110°C, such as at least 120°C, for example at least 130°C, such as at least 140°C, for example at least 150°C, such as at least 160°C, for example at least 170°C, and said second glass transition temperature is higher than -50°C; Conductive base material.

2. 1. A coated conductive substrate comprising an electrodeposited coating deposited from an electrodepositable coating composition, said electrodeposited coating comprising: a platelet-like pigment present in a pigment to binder ratio of at least 0.4:1; an electrodeposited binder, wherein the electrodeposited binder comprises: a first resin domain having a first glass transition temperature of at least 80°C; a second resin domain having a second glass transition temperature of from −50° C. to 70° C.; A conductive substrate comprising:

3. An electrodeposited coating deposited from an electrodepositable coating composition, the electrodeposited coating comprising: a platelet-like pigment present in a pigment to binder ratio of at least 0.4:1; an electrodepositable binder, wherein the electrodepositable binder comprises: a first resin domain having a first glass transition temperature; a second resin domain having a second glass transition temperature, wherein said first glass transition temperature is at least 10°C higher than said second glass transition temperature, such as at least 20°C, for example at least 30°C, such as at least 40°C, for example at least 50°C, such as at least 60°C, for example at least 70°C, such as at least 80°C, for example at least 90°C, such as at least 100°C, for example at least 110°C, such as at least 120°C, for example at least 130°C, such as at least 140°C, for example at least 150°C, such as at least 160°C, for example at least 170°C, and said second glass transition temperature is higher than -50°C; Electrodeposition coating.

4. An electrodeposited coating deposited from an electrodepositable coating composition, the electrodeposited coating comprising: a platelet-like pigment present in a pigment to binder ratio of at least 0.4:1; an electrodepositable binder, wherein the electrodepositable binder comprises: a first resin domain having a first glass transition temperature of at least 80°C; a second resin domain having a second glass transition temperature of from −50° C. to 70° C.; An electrodeposition coating film comprising:

5. 10. The coated conductive substrate or electrodeposition coating of any of the preceding claims, wherein the platelet-shaped pigments have an average equivalent spherical diameter of at least 50 nm.

6. 10. The coated conductive substrate or electrodeposition coating of any preceding claim, wherein the platelet-like pigment comprises a phyllosilicate pigment, optionally wherein the phyllosilicate pigment comprises mica, chlorite, serpentine, talc, a clay mineral, or a combination thereof, optionally wherein the clay mineral comprises kaolin clay, smectite clay, or a combination thereof.

7. 10. The coated conductive substrate or electrodeposition coating according to any preceding claim, wherein the platelet-like pigment is present in a pigment to binder ratio of at least 0.5:1, such as at least 0.6:1, for example at least 0.75:1, such as at least 1:1, for example at least 1.25:1, such as at least 1.5:

1.

8. 10. The coated conductive substrate or electrodeposited coating of any preceding claim, wherein the electrodeposited binder comprises an organic binder, the organic binder comprising residues of an active hydrogen-containing, ionic salt group-containing film-forming polymer, a curing agent, and at least one organic resin component different from the active hydrogen-containing, ionic salt group-containing film-forming polymer and the curing agent.

9. 9. The coated conductive substrate or electrodeposition coating of claim 8, wherein the curing agent comprises an at least partially blocked polyisocyanate, an aminoplast resin, a phenoplast resin, or a combination thereof.

10. the organic resin component is selected from the group consisting of: (1) an addition polymer comprising the polymerization product of a polymerizable dispersant and a second stage ethylenically unsaturated monomer composition comprising second stage hydroxyl-functional (meth)acrylamide monomers and / or second stage hydroxyl-functional (meth)acrylate monomers; and (2) a hydroxyl-functional addition polymer comprising constitutional units, at least 70% of which comprise Formula VIII: _____ １ ) ２ () １ ( In the formula, R １ are each independently 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 percentages are based on the total units of the hydroxyl-functional addition polymer.

11. 11. The coated conductive substrate or electrodeposition coating of any of claims 8 to 10, wherein the organic resin component has a weight average molecular weight of at least 1,000 g / mol.

12. 12. The coated conductive substrate or electrodeposition coating of any of claims 8 to 11, wherein the organic resin component is present in an amount of 0.01 wt % to 50 wt %, based on the total weight of the electrodeposition coating.

13. 13. The coated conductive substrate or electrodeposition coating of any of claims 8 to 12, wherein the organic resin component comprises a hydroxyl-functional addition polymer.

14. 14. The coated conductive substrate or electrodeposition coating of claim 13, wherein the hydroxyl functional addition polymer has a weight average molecular weight of from 5,000 g / mol to 500,000 g / mol.

15. 15. The coated conductive substrate or electrodeposition coating of any of claims 10 to 14, wherein the hydroxyl functional addition polymer is present in an amount of 0.01 wt % to 5 wt %, based on the total weight of the electrodeposition coating.

16. 16. The coated conductive substrate or electrodeposition coating of any of claims 8 to 15, wherein the organic resin component comprises a polyetheramine adduct.

17. 17. The coated conductive substrate or electrodeposition coating of claim 16, wherein the polyetheramine adduct has a weight average molecular weight of from 10,000 g / mol to 500,000 g / mol.

18. 18. The coated conductive substrate or electrodeposition coating of any of claims 10 to 17, wherein the polyetheramine adduct is present in an amount of from 3 wt% to 35 wt%, based on the total weight of the electrodeposition coating.

19. 10. The coated conductive substrate or electrodeposition coating of any preceding claim, wherein the second resin domains are present as visible disturbances in binder homogeneity as determined by TEM analysis.

20. 10. A coated conductive substrate or an electrodeposition coating according to any preceding claim, wherein the second resin domains have a domain size of at least 50 nm, such as at least 100 nm, for example at least 150 nm, such as at least 200 nm, for example at least 250 nm, such as at least 300 nm, for example at least 350 nm, such as at least 400 nm, for example at least 450 nm, such as at least 500 nm, for example at least 550 nm, such as at least 600 nm, for example at least 650 nm, such as at least 700 nm, for example at least 750 nm, such as at least 800 nm.

21. the electrodeposition coating has a peel of less than 15 mm as measured according to the mandrel bend test in accordance with ASTM D522; and / or the electrodeposition coating has an edge coverage of greater than 20% as measured by the Edge Coverage Test Method; and / or The electrodeposition coating film has a water vapor transmission rate of 55 g / m as measured by the water vapor transmission rate test method. ２ / day or less, A coated conductive substrate or electrodeposition coating according to any of the preceding claims.

22. 10. The coated conductive substrate or electrodeposition coating of any preceding claim, wherein the electrodeposition coating further comprises a third glass transition temperature lower than the second glass transition temperature.

23. 23. The coated conductive substrate or electrodeposition coating of claim 22, wherein the third glass transition temperature corresponds to a third resin domain or wherein the third glass transition temperature does not correspond to a third resin domain.

24. 10. The coated conductive substrate or electrodeposition coating of any preceding claim, wherein the coated conductive substrate does not include a pretreatment layer between the substrate and the electrodeposition coating and / or the coated conductive substrate does not include an intervening coating layer between the substrate and the electrodeposition coating.

25. 10. The coated conductive substrate or electrodeposition coating of any preceding claim, wherein the electrodeposition coating further comprises a flame retardant pigment, a hybrid organic-inorganic material, and / or an organic flame retardant additive.

26. an electrodepositable binder comprising an active hydrogen-containing, ionic salt group-containing film-forming polymer, a curing agent, and at least one organic resin component different from the active hydrogen-containing, ionic salt group-containing film-forming polymer and the curing agent; a platelet-like pigment present in a pigment to binder ratio of at least 0.4:

1.

27. 27. The electrodepositable coating composition of claim 26, wherein the platelet-like pigments have an average equivalent spherical diameter of at least 50 nm.

28. 28. The electrodepositable coating composition of claim 26 or 27, wherein the platelet-like pigment comprises a phyllosilicate pigment.

29. 30. The electrodepositable coating composition of claim 28, wherein the phyllosilicate pigment comprises mica, chlorite, serpentine, talc, clay minerals, or combinations thereof.

30. 30. The electrodepositable coating composition of claim 29, wherein the clay mineral comprises a kaolin clay, a smectite clay, or a combination thereof.

31. 31. The electrodepositable coating composition of any of claims 26 to 30, wherein the platelet-like pigment is present in a pigment to binder ratio of at least 0.5:1, such as at least 0.6:1, for example at least 0.75:1, such as at least 1:1, for example at least 1.25:1, such as at least 1.5:

1.

32. 32. The electrodepositable coating composition of any of claims 26 to 31, wherein the curing agent comprises an at least partially blocked polyisocyanate, an aminoplast resin, a phenoplast resin, or a combination thereof.

33. the organic resin component is selected from the group consisting of: (1) an addition polymer comprising the polymerization product of a polymerizable dispersant and a second stage ethylenically unsaturated monomer composition comprising second stage hydroxyl-functional (meth)acrylamide monomers and / or second stage hydroxyl-functional (meth)acrylate monomers; (2) a hydroxyl-functional addition polymer comprising constitutional units, at least 70% of which comprise Formula VIII: _____ １ ) ２ () １ ( In the formula, R １ are each independently 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 percentages are based on all units of the hydroxyl-functional addition polymer.

34. 34. The electrodepositable coating composition of any of claims 26 to 33, wherein the organic resin component has a weight average molecular weight of at least 1,000 g / mol.

35. 35. The electrodepositable coating composition of any of claims 26 to 34, wherein the organic resin component is present in an amount of 0.01 wt % to 50 wt %, based on the total weight of resin solids of the electrodepositable coating composition.

36. 36. The electrodepositable coating composition of any of claims 26 through 35, wherein the organic resin component comprises a hydroxyl-functional addition polymer.

37. 37. The electrodepositable coating composition of claim 36, wherein the hydroxyl-functional addition polymer has a weight average molecular weight of from 5,000 g / mol to 500,000 g / mol.

38. 38. The electrodepositable coating composition of any of claims 33 through 37, wherein the hydroxyl-functional addition polymer is present in an amount of 0.01 wt % to 5 wt %, based on total weight of resin solids of the electrodepositable coating composition.

39. 38. The electrodepositable coating composition of any of claims 26 to 37, wherein the organic resin component comprises a polyetheramine adduct.

40. 40. The electrodepositable coating composition of claim 39, wherein the polyetheramine adduct has a weight average molecular weight of 10,000 g / mol to 500,000 g / mol.

41. 41. The electrodepositable coating composition of any of claims 33 to 40, wherein the polyetheramine adduct is present in an amount of 3 wt% to 35 wt%, based on the total weight of resin solids of the electrodepositable coating composition.

42. 42. The electrodepositable coating composition of any of claims 26 to 41, further comprising a flame retardant pigment, a hybrid organic-inorganic material, and / or an organic flame retardant additive.

43. 43. A method of coating an electrically conductive substrate comprising electrophoretically applying a coating deposited from the electrodepositable coating composition of any of claims 26 to 42 to at least a portion of the electrically conductive substrate.

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