Electrodeposition coatings with multiple resin domains

Abstract

The present disclosure relates to an electrodeposited coating or a coated metal substrate comprising the electrodeposited coating wherein the electrodeposited coating comprises: a plate-like pigment present in a pigment to binder ratio of at least 0.4: 1; and an electrodeposition binder comprising: a first resin domain 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 DEG C greater than the second glass transition temperature, and the second glass transition temperature is greater than-50 DEG C, and / or the first glass transition temperature is at least 80 DEG C, and / or the second glass transition temperature is greater than-50 DEG C. And the second glass transition temperature is from-50 DEG C to 70 DEG C. An electrodepositable coating composition and a method of coating a substrate are also disclosed.

Description

Technical Field

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

[0002] As a coating application method, electrodeposition involves depositing a film-forming composition onto a conductive substrate under the influence of an applied electric potential. Compared to non-electrophoretic coating methods, electrodeposition is becoming increasingly popular in the coating industry due to its higher coating utilization, excellent corrosion resistance, and low environmental pollution. 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 the electrodeposition coating, wherein the electrodeposition coating comprises: a plate-like pigment present in a pigment to binder ratio of at least 0.4:1; and an electrodeposition binder comprising: a first resin domain 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 greater than the second glass transition temperature, such as at least 20°C, such as at least 30°C, such as at least 40°C, such as at least 50°C, such as at least 60°C, such as at least 70°C, such as at least 80°C, such as at least 90°C, such as at least 100°C, such as at least 110°C, such as at least 120°C, such as at least 130°C, such as at least 140°C, such as at least 150°C, such as at least 160°C, such as at least 170°C, and the second glass transition temperature is greater than -50°C.

[0004] The present disclosure also provides an electrodeposition coating or a coated conductive substrate comprising the electrodeposition coating, wherein the electrodeposition coating comprises: a platy pigment present in a pigment to binder ratio of at least 0.4:1; and an electrodeposition 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, the at least one organic resin component being different from the active hydrogen-containing, ionic salt group-containing film-forming polymer and the curing agent; and a platy pigment, the platy pigment being 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, the method 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; and at least one organic resin component, the at least one organic resin component being different from the active hydrogen-containing, ionic salt group-containing film-forming polymer and the curing agent; and a platy pigment, the platy pigment being present in a pigment to binder ratio of at least 0.4:1. BRIEF DESCRIPTION OF THE DRAWINGS

[0007] Figure 1 is a compilation of TEM images of the electrodeposited coatings described in Examples 1-5. DETAILED DESCRIPTION

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

[0009] The present disclosure also relates to an electrodeposition coating or a coated conductive substrate comprising the electrodeposition coating, wherein the electrodeposition coating comprises: a platy pigment present in a pigment to binder ratio of at least 0.4:1; and an electrodeposition 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, the at least one organic resin component being different from the active hydrogen-containing, ionic salt group-containing film-forming polymer and the curing agent; and a platy pigment, the platy pigment being present in a pigment to binder ratio of at least 0.4:1.

[0011] Plate-shaped pigments

[0012] The electrodeposited coating and / or electrodepositable coating composition comprises a platy pigment present in a pigment to binder ratio of at least 0.4:1.

[0013] The platy pigment may be an inorganic platy pigment.

[0014] The plate-like pigment may be a phyllosilicate pigment. As used herein, the term "phyllosilicate" refers to a group of minerals having silicate sheets, the basic structure of which is based on interconnected SiO4 -4 The six-membered ring of the tetrahedron extends outward in an infinite layer, where three of the four oxygens of each tetrahedron are shared with other tetrahedrons, thus producing the basic structural unit Si2O5 -2 The layered silicate may contain hydroxide ions and / or cations located at the tetrahedral centers, such as, for example, Fe +2 Mg +2 or Al +3 , these ions form cationic layers between the silicate sheets, wherein the cations can coordinate with the oxygen and / or hydroxide ions of the silicate layers. The term "phyllosilicate pigment" refers to a pigment material comprising phyllosilicates. Non-limiting examples of phyllosilicate pigments include mica, chlorite, serpentine, talc, and clay minerals. Clay minerals include, for example, kaolin clay and montmorillonite clay. The sheet-like structure of phyllosilicate pigments tends to give the pigments a plate-like structure, but the pigments can be manipulated (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 have leachable components (e.g., ions that may be attracted to the liquid medium).

[0015] The platy silicate pigment may include platy mica pigment, platy chlorite pigment, platy serpentine pigment, platy talc pigment and / or platy clay pigment. The platy clay pigment may include kaolin clay, montmorillonite clay or a combination thereof.

[0016] Pigment component comprises plate-like pigment, and it can have at least 50nm and up to 25 microns or higher average equivalent spherical diameter.Average equivalent spherical diameter can use dynamic light scattering to measure, such as utilizing the SEDIGRAPHIIIPLUS particle size analyzer that can obtain from MicromeriticsInstrumentCorp.As plate-like particle, pigment has substantially relative surface usually, and particle shows for example at least 2:1 longest axis and the aspect ratio of shortest axis usually.For example, plate-like pigment can have at least 50nm, such as at least 0.2 micron, such as at least 0.4 micron, such as at least 0.6 micron, 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 average equivalent spherical diameter.Plate-like pigment can have and be no more than 25 microns, such as no more than 15 microns, such as no more than 10 microns, such as no more than 5 microns, such as no more than 3.5 microns, such as no more than 2.5 microns, such as no more than 1.9 microns, such as no more than 1.5 microns, such as no more than 1 micron average equivalent spherical diameter.

[0017] The pigment to binder (P: B) ratio described in the present disclosure may refer to the weight ratio of the pigment to the binder in the electrodepositable coating composition, and / or the weight ratio of the pigment to the binder in the deposited wet film, and / or the weight ratio of the pigment to the binder in the dried uncured deposited film, and / or the weight ratio of the pigment to the binder in the cured film (i.e., the electrodeposited coating). The pigment to binder (P: B) ratio of the pigment to the electrodepositable binder may be at least 0.4: 1, such as at least 0.5: 1, such as at least 0.6: 1, such as at least 0.75: 1, such as at least 1: 1, such as at least 1.25: 1, such as at least 1.5: 1. The pigment to the electrodepositable binder or the electrodeposition binder may have a pigment to binder (P:B) ratio of no more than 2:1, such as no more than 1.75:1, such as no more than 1.5:1, such as no more than 1.25:1, such as no more than 1:1, such as no more than 0.75:1, such as no more than 0.7:1, such as no more than 0.6:1, such as no more than 0.55:1, such as no more than 0.5:1. The pigment to the electrodepositable binder or the electrodeposition binder may have a pigment to binder (P:B) ratio of 0.4:1 to 2:1, such as 0.4:1 to 1.75:1, such as 0.4:1 to 1.5:1, such as 0.4:1 to 1.25:1, such as 0.4:1 to 1:1, such as 0.4:1 to 0.75:1, such as 0.4:1 to 0.7:1, such as 0.4:1 to 0.6:1, such as 0. 0.4:1 to 0.55:1, such as 0.4:1 to 0.5:1, such as 0.5:1 to 2:1, such as 0.5:1 to 1.75:1, such as 0.5:1 to 1.50:1, such as 0.5:1 to 1.25:1, such as 0.5:1 to 1:1, such as 0.5:1 to 0.75:1, such as 0.5:1 to 0.7:1, such as 0.5:1 to 0.6:1, such as 0.5:1 to 0 .55:1, such as 0.6:1 to 2:1, such as 0.6:1 to 1.75:1, such as 0.6:1 to 1.5:1, such as 0.6:1 to 1.25:1, such as 0.6:1 to 1:1, such as 0.6:1 to 0.75:1, such as 0.6:1 to 0.7:1, such as 0.75:1 to 2:1, such as 0.75:1 to 1.75:1, such as 0.75:1 to 1.5:1, Such as 0.75:1 to 1.25:1, such as 0.75:1 to 1:1, such as 1:1 to 2:1, such as 1:1 to 1.75:1, such as 1:1 to 1.5:1, such as 1:1 to 1.25:1, such as 1.25:1 to 2:1, such as 1.25:1 to 1.75:1, such as 1.25:1 to 1.5:1, such as 1.5:1 to 2:1, such as 1.5:1 to 1.75:1.

[0018] Resin domain

[0019] As used herein, the term "resin domain" in the first resin domain or the second resin domain refers to a visible disruption of the uniformity of the adhesive. The visible disruption may be visible using a 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 that is phase-separated from the bulk resin. For example, the second resin domain may be a resin dispersion capsule dispersed throughout the bulk resin of the first resin domain. The resin dispersion capsule may have any geometric shape or morphology, such as, for example, spherical, lamellar, cylindrical, and the like. The dispersion capsules may be dispersed approximately uniformly, or may be dispersed inconsistently. The dispersion capsules may also be layered throughout the bulk resin. Alternatively, the first resin domain and the second resin domain may phase-separate into a double-layer configuration, wherein one of the resin domains is present on the surface of the substrate, and the other resin domain is present on top of the domain. The resin domains typically do not contain plate-like pigments.

[0020] As mentioned above, visible destruction can be visible using TEM. The identification of the second resin domain can be determined according to the following method, which will be mentioned in the TEM analysis method in this article: the coated and cured panel is cut into a certain size and embedded in EMBed-812 epoxy resin and cured at 60°C for 24 hours. Thin slices (<80nm) are then ultramicrotomed and collected on Cu TEM grids. Bright field images are taken on a Tecnai T20 TEM operated at 200kV. Visible resin domains can be identified in the resulting TEM images. Further image analysis can be performed to determine the size of the resin domain, as discussed in the Examples section below.

[0021] The first resin domain has a first glass transition temperature, and the second resin domain has a second glass transition temperature. The first glass transition temperature may be at least 10°C greater than the second glass transition temperature, such as at least 20°C, such as at least 30°C, such as at least 40°C, such as at least 50°C, such as at least 60°C, such as at least 70°C, such as at least 80°C, such as at least 90°C, such as at least 100°C, such as at least 110°C, such as at least 120°C, such as at least 130°C, such as at least 140°C, such as at least 150°C, such as at least 160°C, such as at least 170°C, and the second glass transition temperature is greater than -50°C.

[0022] The first glass transition temperature may be at least 80° C., such as at least 90° C., such as at least 100° C., such as at least 110° C., such as at least 120° C., such as at least 125° C. The first glass transition temperature may be no more than 130° C., such as no more than 120° C., such as no more than 110° C., such as no more than 100° C., such as no more than 90° C. The first glass transition temperature may be 80° C. to 130° C., such as 80° C. to 120° C., such as 80° C. to 110° C., such as 80° C. to 100° C., such as 80° C. to 90° C., such as 90° C. to 130° C., such as 90° C. to 120° C., such as 90° C. to 110° C., such as 90° C. to 100° C., such as 100° C. to 130° C., such as 100° C. to 120° C., such as 100° C. to 110° C., such as 110° C. to 130° C., such as 110° C. to 120° C., such as 120° C. to 130° C.

[0023] The second glass transition temperature may be at least -50°C, such as at least -40°C, such as at least -30°C, such as at least -20°C, such as at least -10°C, such as at least 0°C, such as at least 10°C, such as at least 20°C, such as at least 30°C, such as at least 40°C, such as at least 50°C, such as at least 60°C. The second glass transition temperature may be no more than 70°C, such as no more than 50°C, such as no more than 30°C, such as no more than 10°C, such as no more than 0°C, such as no more than -10°C, such as no more than -20°C, such as no more than -30°C. The second glass transition temperature may be -50°C to 70°C, such as -50°C to 50°C, such as -50°C to 30°C, such as -50°C to 10°C, such as -50°C to 0°C, such as -50°C to -10°C, such as -50°C to -20°C, such as -50°C to -30°C, such as -40°C to 70°C, such as -40°C to 50°C, such as -40°C to 30°C, such as -40°C to 10°C, such as -40°C to 0°C, such as -40°C to -10°C, such as -40°C to -20°C, such as -40°C to -30°C, such as -30°C to 70°C, such as -30°C to 50°C, such as -30°C to 30°C, such as -30°C to 10°C, such as -30°C to 0°C, such as -30°C to -10°C, such as -30°C to -20°C, such as -2 0℃ to 70℃, such as -20℃ to 50℃, such as -20℃ to 30℃, such as -20℃ to 10℃, such as -20℃ to 0℃, such as -20℃ to -10℃, such as -10℃ to 70℃, such as -10℃ to 50℃, such as -10℃ to 30℃, such as -10℃ to 10℃, such as -10℃ to 0℃, such as 0℃ to 70℃, such as 0℃ to 50℃, such as 0℃ to 30℃, such as 0℃ to 10℃, such as 10℃ to 70℃, such as 10℃ to 50℃, such as 10℃ to 30℃, such as 20℃ to 70℃, such as 20℃ to 50℃, such as 20℃ to 30℃, such as 30℃ to 70℃, such as 30℃ to 50℃, such as 40℃ to 70℃, such as 40℃ to 50℃, such as 50℃ to 70℃, such as 60℃ to 70℃.

[0024] The second resin domain 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 the resin domain refers to a measurement result obtained according to the following procedure: a coated and cured panel is cut to size and embedded in EMBed-812 epoxy resin and cured at 60°C for 24 hours. Thin slices (<80 nm) are then ultramicrotomed and collected on Cu TEM grids. Bright field images are taken on a Tecnai T20 TEM operating at 200 kV. The maximum Feret diameter of the low-density domains was determined by measuring 10 domains in three different images using ImageJ.

[0025] The electrodeposited coating optionally may further comprise a third glass transition temperature, and if present, the third glass transition temperature may or may not correspond to the presence of third resin domains. If present, the third glass transition temperature may be less than -50°C.

[0026] The glass transition temperature can be measured according to the procedure described in the Examples section.

[0027] Electrodepositable adhesives

[0028] 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 resin material that can be applied to the electrodepositable coating composition to enable the electrodepositable coating composition to be applied by an electrodeposition process.

[0029] As used herein, the term "electrodepositable coating composition" refers to a composition capable of being deposited onto a conductive substrate under the influence of an electric potential applied between two electrodes immersed in the electrodepositable coating composition, wherein one of the electrodes is the substrate to be coated.

[0030] The electrodepositable coating composition comprises an electrodepositable binder, which may include any suitable electrodepositable binder. For example, the electrodepositable binder may include an organic and / or inorganic electrodepositable binder. As used herein, the term "binder" refers to the non-volatile components of the electrodepositable coating composition other than the filler.

[0031] As used herein, an "organic" electrodepositable binder may include a film-forming polymer and / or curing agent comprising a carbon-based material. As used herein, an "inorganic" electrodepositable binder may include a film-forming polymer and / or curing agent based on other materials (such as, for example, silicone-based materials). It should be understood that the electrodepositable binder may also include a mixture of organic and inorganic film-forming and / or curing agent materials.

[0032] 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 are capable of forming a film when reacted with a curing agent or cross-linking agent. As used herein, the term "crosslinker," "crosslinking agent," or "curing agent" refers to a molecule that is capable of forming covalent bonds between polymers. For example, a polyisocyanate curing agent can react with active hydrogen groups on a film-forming polymer to achieve at least partial curing of the coating composition to form a coating. As used herein, the term "curing," "cured," or similar terms means that at least a portion of the coating composition is cross-linked to form a coating.

[0033] The electrodepositable coating composition may comprise a film-forming polymer containing ionic salt groups, such as a film-forming polymer containing cationic salt groups or a film-forming polymer containing anionic salt groups.

[0034] For example, a film-forming polymer containing an ionic salt group may include the reaction product of a reaction mixture consisting of: (a) a polyepoxide; (b) a difunctional chain extender; and (c) a monofunctional reactant. Non-limiting examples of such polymers are provided in International Application No. PCT / US22 / 73356, paragraphs

[0023] to

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

[0035] As used herein, the term "film-forming polymer containing cationic salt groups" 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 film-forming polymer containing cationic salt groups may include active hydrogen functional groups. As used herein, the term "active hydrogen functional groups" refers to those groups that react with isocyanates and include, for example, hydroxyl groups, primary or secondary amine groups, carbamates, and thiol groups.

[0036] 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, and adducts, derivatives, and combinations thereof.

[0037] The film-forming polymer containing cationic salt groups is 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 aminosulfonic acid.

[0038] The degree of neutralization of the film-forming polymer containing cationic salt groups can vary depending on the specific polymer involved. However, sufficient acid should be used to fully neutralize the film-forming polymer containing cationic salt groups so that the film-forming polymer containing cationic salt groups can be dispersed in the aqueous dispersion medium. For example, the amount of acid used can provide at least 20% of the total theoretical neutralization. Alternatively, the amount of acid used can provide more than 100% of the total theoretical neutralization. The total amount of acid used to neutralize the film-forming polymer containing cationic salt groups can be between any combination of values, such as 20% or more to such as greater than 100%, including the stated values. For example, based on the total amines in the film-forming polymer containing cationic salt groups, the total amount of acid used to neutralize the active hydrogen-containing, film-forming polymer containing cationic salt groups can be 20%, 35%, 50%, 60%, 80% or 100% or more.

[0039] As used herein, the term "film-forming polymer containing anionic salt groups" refers to an anionic polymer containing at least partially neutralized anionic functional groups such as carboxylic acid groups and / or phosphoric acid groups that impart a negative charge. The film-forming polymer containing anionic salt groups may include active hydrogen functional groups.

[0040] Non-limiting examples of polymers suitable for use as film-forming polymers containing anionic salt groups for electrodepositable binders include, but are not limited to, dry and / or semi-dry and / or saturated alkyd polymers, acrylics, polyepoxides, polyamides, polyurethanes, polyureas, polyethers, polyesters, resin polyols, phosphated polyepoxides and phosphated acrylic polymers, carriers comprising alkyd resins and amine aldehydes, and adducts, derivatives and combinations thereof.

[0041] 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. WO 2021 / 138384 A1, paragraphs

[0007] to

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

[0042] 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 %, such as at least 20 wt %, such as at least 25 wt %, such as at least 30 wt %, such as at least 35 wt %, such as at least 40 wt %, based on the total weight of the active hydrogen-containing, ionic salt group-containing film-forming polymer.

[0043] As used herein, the term "aromatic content" refers to π-bond resonance structures, where, according to molecular orbital theory, the number of π electrons is equal to 4n+2, where n=1, 2, 3, etc. A non-limiting example of a cyclic aromatic structure is a benzene ring having six π electrons and n=1. The weight percent aromatic content of a polymer is determined by including only the atoms within the aromatic structure; for example, for a benzene ring, only the six carbon atoms in the ring contribute to the aromatic content of the polymer.

[0044] The film-forming polymer containing ionic salt groups 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 the resin solids of the electrodepositable coating composition. The film-forming polymer containing ionic salt groups may be present in the electrodepositable coating composition in an amount of no more than 90 wt %, such as no more than 80 wt %, such as no more than 75 wt %, based on the total weight of the resin solids of the electrodepositable coating composition. The film-forming polymer containing ionic salt groups can be present in the electrodepositable coating composition in an amount of 40 wt % to 90 wt %, such as 40 wt % to 80 wt %, such as 40 wt % to 75 wt %, such as 50 wt % to 90 wt %, such as 50 wt % to 80 wt %, such as 50 wt % to 75 wt %, such as 55 wt % to 90 wt %, such as 55 wt % to 80 wt %, such as 55 wt % to 75 wt %, such as 60 wt % to 90 wt %, such as 60 wt % to 80 wt %, such as 60 wt % to 75 wt %, based on the total weight of the resin solids of the electrodepositable coating composition.

[0045] As used herein, "resin solids" include the ionic salt group-containing film-forming polymer, the curing agent, and any additional water-dispersible, unpigmented components present in the electrodepositable coating composition.

[0046] The electrodepositable coating composition of the present disclosure may further comprise a curing agent. The curing agent may react with the reactive groups (such as active hydrogen groups) of the film-forming polymer containing ionic salt groups and any reactive groups (if present) of any additional resin material to achieve curing of the electrodepositable coating composition to 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 allyl ether derivatives thereof.

[0047] As used herein, "blocked polyisocyanate" refers to a polyisocyanate in which at least a portion of the isocyanate groups are blocked by blocking groups introduced by reaction of the free isocyanate groups of the polyisocyanate with a blocking agent. "Blocked" means that the isocyanate groups have reacted with the blocking agent such that the resulting blocked isocyanate groups are stable to active hydrogen at ambient temperature (e.g., room temperature (23°C)). This reaction can be reversed under appropriate conditions, such as at elevated temperatures (such as, for example, between 90°C and 200°C), such that the previously blocked isocyanate groups on the polyisocyanate curing agent are unblocked and can react with the reactive groups (such as active hydrogen groups) of the film-forming polymer containing ionic salt groups to effect curing of the coating composition to form a coating.

[0048] As used herein, "blocking agent" refers to a compound containing a functional group that can react with an isocyanate group to form a blocked isocyanate. As used herein, "blocking group" refers to the remaining portion of the blocking agent that is bound to the isocyanate group in the blocked polyisocyanate.

[0049] The blocking agent separated from the blocked polyisocyanate curing agent during curing can be removed from the coating film by volatilization. Alternatively, a portion or all of the blocking agent can remain in the coating film after curing.

[0050] Non-limiting examples of blocked polyisocyanate curing agents and amounts thereof, including suitable polyisocyanates and blocking components (such as blocking groups and / or blocking agents), such as, but not limited to, 1,2 polyols, are provided in International Publication No. WO 2021 / 138583 A1, paragraphs

[0022] to

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

[0051] Non-limiting examples of blocked polyisocyanates comprising blocking groups derived from a blocking agent (comprising an α-hydroxyamide, ester, or thioester) and optionally a second blocking agent are provided in International Publication No. WO 2018 / 148306 A1, paragraphs

[0010] to

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

[0052] The at least partially blocked polyisocyanate may be partially blocked with one or more of the blocking groups discussed above, wherein the remaining isocyanate groups react with the polymer backbone, such as described in U.S. Pat. No. 3,947,338, at column 2, line 65 to column 5, line 33, the cited portions of which are incorporated herein by reference.

[0053] 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)-, tris(butoxycarbonylamino)-, and tris(2-ethylhexyloxycarbonylamino)-1,3,5-triazines, and any combination thereof.

[0054] The curing agent may include an aminoplast resin or a phenoplast resin. An aminoplast resin is a condensation product of an aldehyde with a substance carrying an amino or amide group. A phenoplast resin is formed by the condensation of an aldehyde and a phenol.

[0055] Non-limiting examples of commercially available aminoplast resins are those sold under the trademark GLUTAMATE® from Allnex Belgium SA / NV. (such as CYMEL 1130 and 1156) and from INEOS Melamines under the trademark Aminoplast resins such as those commercially available from RESIMENE 750 and 753. Examples of suitable aminoplast resins and amounts thereof also include those described in U.S. Patent No. 3,937,679 at column 16, line 3 to column 17, line 47, this portion of which is hereby incorporated by reference. As disclosed in the preceding portion of the '679 patent, aminoplasts can be used in combination with methanol phenol ethers.

[0056] Suitable aminoplast resins and phenoplast resins are also further described in US Pat. No. 4,812,215 at column 6, line 20 to column 7, line 12, the cited portions of which are incorporated herein by reference.

[0057] Non-limiting examples of other curing agents include silicone-based curing agents. Non-limiting examples of such curing agents are described in International Publication No. WO 2021 / 138384 A1, paragraphs

[0030] to

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

[0058] Based on the total weight of the resin solids of the electrodepositable coating composition, the curing agent may be present in the electrodepositable coating composition in an amount of at least 10 wt %, such as at least 20 wt %, such as at least 25 wt %. Based on the total weight of the resin solids of the electrodepositable coating composition, the curing agent may be present in the electrodepositable coating composition in an amount of no more than 60 wt %, such as no more than 50 wt %, such as no more than 45 wt %, such as no more than 40 wt %. Based on the total weight of the resin solids of the electrodepositable coating composition, the curing agent may be present in the electrodepositable coating composition in an amount of 10 wt % to 60 wt %, such as 10 wt % to 50 wt %, such as 10 wt % to 45 wt %, such as 10 wt % to 40 wt %, such as 20 wt % to 60 wt %, such as 20 wt % to 50 wt %, such as 20 wt % to 45 wt %, such as 20 wt % to 40 wt %, such as 25 wt % to 60 wt %, such as 25 wt % to 50 wt %, such as 25 wt % to 45 wt %, such as 25 wt % to 40 wt %.

[0059] According to the present disclosure, the electrodepositable coating and / or electrodepositable coating composition may optionally further comprise a curing catalyst. As used herein, the terms "curing catalyst" and "catalyst" are used interchangeably and refer to a material that catalyzes the curing reaction between the components of the electrodepositable coating composition (such as, for example, the curing agent and the film-forming polymer). For example, the catalyst can catalyze the urethanization reaction, and in particular, catalyze the deblocking of blocked polyisocyanate blocking groups.

[0060] Non-limiting examples of curing catalysts include: amine-containing compounds; compounds or complexes of metals such as bismuth, cerium, zinc, and / or titanium; and combinations thereof.

[0061] Catalysts suitable for use in the cationic electrodepositable coating compositions include, but are not limited to, metal oxides (e.g., oxides of cerium, zirconium, and bismuth) and their salts; zinc compounds or complexes; and / or cyclic guanidines, such as those described in U.S. Patent No. 7,842,762 at column 1, line 53 to column 4, line 18 and column 16, line 62 to column 19, line 8, the cited portions of which are incorporated herein by reference.

[0062] Catalysts suitable for use in anionic electrodepositable coating compositions include, but are not limited to, latent acid catalysts. Latent acid catalysts are derivatives of acid catalysts typically activated by heating. Non-limiting examples of latent acid catalysts are identified in WO 2007 / 118024 paragraph

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

[0063] The amine-containing curing catalyst may include any suitable amine-containing curing catalyst, such as, but not limited to, a curing catalyst comprising guanidine, imidazole, amidine, and / or derivatives or combinations thereof.

[0064] Non-limiting examples of suitable guanidine curing catalysts are provided in International Publication No. WO 2018 / 0172519 A1, paragraphs

[0039] to

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

[0065] Non-limiting examples of imidazole cure catalysts are described in U.S. Publication No. 2022 / 0154014 Al, paragraphs

[0062] to

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

[0066] A non-limiting example of an amidine cure catalyst may include 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0067] The zinc-containing catalyst may include a metal salt and / or complex of zinc, such as, but not limited to, zinc (II) amidine complexes, zinc octoate, zinc naphthenate, zinc tall oleate, zinc carboxylates (having 8 to 14 carbons in the carboxylate group), zinc acetate, zinc sulfonate, zinc methanesulfonate, or any combination thereof. The zinc (II) amidine complex may contain an amidine and a carboxylate ligand.

[0068] The curing catalyst can be present in the electrodepositable coating composition in any suitable amount. For example, based on the gross weight of the resin solids in the coating composition, the amine-containing curing catalyst and / or the zinc-containing curing catalyst can be present in the coating composition in an amount of at least 0.1 wt %, such as at least 0.2 wt %, such as at least 0.5 wt %, such as at least 0.8 wt %, such as at least 1 wt %, such as at least 1.5 wt %. Based on the gross weight of the resin solids in the coating composition, the amine-containing curing catalyst and / or the zinc-containing curing catalyst can be present in the coating composition in an amount of no more than 7 wt %, such as no more than 4 wt %, such as no more than 2 wt %, such as no more than 1.5 wt %, such as no more than 1 wt %. The amine-containing curing catalyst and / or the zinc-containing curing catalyst may be present in the coating composition in an amount of 0.1 wt % to 7 wt %, such as 0.1 wt % to 4 wt %, such as 0.1 wt % to 2 wt %, such as 0.1 wt % to 1.5 wt %, such as 0.1 wt % to 1 wt %, such as 0.2 wt % to 7 wt %, such as 0.2 wt % to 4 wt %, such as 0.2 wt % to 2 wt %, such as 0.2 wt % to 1.5 wt %, such as 0.2 wt % to 1 wt %, such as 0.5 wt % to 7 wt %, such as 0.5 wt % to 4 wt%, such as 0.5 wt% to 2 wt%, such as 0.5 wt% to 1.5 wt%, such as 0.5 wt% to 1 wt%, such as 0.8 wt% to 7 wt%, such as 0.8 wt% to 4 wt%, such as 0.8 wt% to 2 wt%, such as 0.8 wt% to 1.5 wt%, such as 0.8 wt% to 1 wt%, such as 1 wt% to 7 wt%, such as 1 wt% to 4 wt%, such as 1 wt% to 2 wt%, such as 1 wt% to 1.5 wt%, such as 1.5 wt% to 7 wt%, such as 1.5 wt% to 4 wt%, such as 1.5 wt% to 2 wt%.

[0069] The curing catalyst may include a bismuth catalyst. Non-limiting examples of bismuth curing catalysts and amounts thereof are described in International Publication No. WO 2021 / 138583 A1, paragraphs

[0036] to

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

[0070] The curing catalyst may include titanium compounds and / or complexes such as, for example, Ti(OR 1 )4, where R 1 is an alkyl or aryl group, such as where R 1 is a C3-C20 alkyl group, such as wherein R 1 is n-butyl, such as tetrabutyl titanate.

[0071] The electrodepositable coating composition may be substantially free, substantially free, or completely free of catalytic tin. The electrodepositable coating composition may be substantially free, substantially free, or completely free of catalytic tin. As used herein, an electrodepositable coating composition is "substantially free" of catalytic tin if the catalytic tin is present in an amount of less than 0.1 weight percent, based on the total weight of the electrodepositable coating composition. As used herein, an electrodepositable coating composition is "substantially free" of catalytic tin if the catalytic tin is present in an amount of less than 0.01 percent, based on the total weight of the electrodepositable coating composition. As used herein, an electrodepositable coating composition is "completely free" of catalytic tin if the catalytic tin is present in an amount of 0.001 percent, based on the total weight of the electrodepositable coating composition.

[0072] Organic resin component

[0073] 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.

[0074] As used herein, "organic resin component" refers to an organic-based polymer component.

[0075] The organic resin component may have a weight average molecular weight of at least 1,000 g / mol or more.

[0076] Based on the total weight of the electrodeposition coating and / or the electrodepositable adhesive, 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 electrodeposition coating and / or the electrodepositable adhesive, the organic resin component may be present in an amount of not more than 50 wt %, such as not more than 35 wt %, such as not more than 30 wt %, such as not more than 25 wt %, such as not more than 20 wt %, such as not more than 15 wt %, such as not more than 10 wt %, such as not more than 5 wt %, such as not more than 3 wt %, such as not more than 2 wt %, such as not more than 1.5 wt %, such as not more than 1 wt %, such as not more than 0.75 wt %. Based on the total weight of the electrodeposition coating and / or the electrodepositable adhesive, the organic resin component may be present in an amount of 0.01 wt % to 50 wt %, such as 0.01 wt % to 35 wt %, such as 0.01 wt % to 30 wt %, such as 0.01 wt % to 25 wt %, such as 0.01 wt % to 20 wt %, such as 0.01 wt % to 15 wt %, such as 0.01 wt % to 10 wt %, such as 0.01 wt % to 5 wt %, such as 0.01 wt % to 3 wt %, such as 0.01 wt % to 2 wt %, such as 0.01 wt % to 1.5 wt %, such as 0.01 wt % to 1 wt %, such as 0.01 wt % to 0.75 wt %, such as 0.1 wt % to 50 wt %, such as 0.1 wt % to 35 wt %, such as 0.1 wt % to 30 wt %, such as 0.1 wt % to 25 wt %, such as 0.1 wt % to 20 wt %, such as 0.1 wt % to 15 wt %, Such as 0.1 wt % to 10 wt %, such as 0.1 wt % to 5 wt %, such as 0.1 wt % to 3 wt %, such as 0.1 wt % to 2 wt %, such as 0.1 wt % to 1.5 wt %, such as 0.1 wt % to 1 wt %, such as 0.1 wt % to 0.75 wt %, such as 0.3 wt % to 35 wt %, such as 0.3 wt % to 30 wt %, such as 0.3 wt % to 25 wt %, such as 0.3 wt % to 20 wt %, such as 0.3 wt % to 15 wt %, such as 0.3 wt % to 10 wt %, such as 0.3 wt % to 5 wt %, such as 0.3 wt % to 3 wt %, such as 0.3 wt % to 2 wt %, such as 0.3 wt % to 1.5 wt %, such as 0.3 wt % to 1 wt %, such as 0.3 wt % to 0.75 wt %, such as 0.5 wt % to 50 wt %, such as 0.5 wt % to 35 wt %, such as 0.5 wt % to 30 wt %, such as 0.5 wt % to 25 wt %, such as 0.5 wt % to 20 wt %, such as 0.5 wt % to 15 wt %, such as 0.5 wt % to 10 wt %, such as 0.5 wt % to 5 wt %, such as 0.5 wt % to 3 wt %, such as 0.5 wt % to 2 wt %, such as 0.5 wt % to 1.5 wt %, such as 0.5 wt % to 1 wt %, such as 0.5 wt % to 0.75 wt %, such as 1 wt % to 50 wt %, such as 1 wt % to 35 wt %, such as 1 wt % to 30 wt % , such as 1 wt % to 25 wt %, such as 1 wt % to 20 wt %, such as 1 wt % to 15 wt %, such as 1 wt % to 10 wt %, such as 1 wt % to 5 wt %, such as 1 wt % to 3 wt %, such as 1 wt % to 2 wt %, such as 1 wt % to 1.5 wt %, such as 3 wt % to 50 wt %, such as 3 wt % to 35 wt %, such as 3 wt % to 30 wt %, such as 3 wt % to 25 wt %, such as 3 wt % to 20 wt %, such as 3 wt % to 15 wt %, such as 3 wt % to 10 wt %, such as 3 wt % to 5 wt %, such as 5 wt % to 50 wt %, such as 5 wt % to 35 wt %, such as 5 wt % to 30 wt %, such as 5 wt % to 25 wt %, such as 5 wt % to 20 wt %, such as 5 wt % to 15 wt %, such as 5 wt % to 10 wt %, such as 10 wt % to 50 wt %, such as 10 wt % to 35 wt %, such as 10 wt % to 30 wt %, such as 10 wt % to 25 wt %, such as 10 wt % to 20 wt % , such as 10 wt % to 15 wt %, such as 15 wt % to 50 wt %, such as 15 wt % to 35 wt %, such as 15 wt % to 30 wt %, such as 15 wt % to 25 wt %, such as 15 wt % to 20 wt %, such as 20 wt % to 50 wt %, such as 20 wt % to 35 wt %, such as 20 wt % to 30 wt %, such as 20 wt % to 25 wt %, such as 25 wt % to 50 wt %, such as 25 wt % to 35 wt %, such as 25 wt % to 30 wt %.

[0077] Non-limiting examples of suitable organic resin components include: (1) an addition polymer comprising the polymerization product of a polymeric dispersant and a second-stage ethylenically unsaturated monomer composition comprising a second-stage hydroxy-functional (meth)acrylamide monomer and / or a second-stage hydroxy-functional (meth)acrylate monomer; and (2) a hydroxy-functional addition polymer comprising structural units, at least 70% of which comprise Formula VIII:

[0078] —[—C(R 1 )2—C(R 1)(OH)—]—(VIII),

[0079] Each R 1 is independently one of hydrogen, an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an alkylcycloalkyl group, a substituted alkylcycloalkyl group, a cycloalkylalkyl group, a substituted cycloalkylalkyl group, an aryl group, a substituted aryl group, an alkylaryl group, a substituted alkylaryl group, a cycloalkylaryl group, a substituted cycloalkylaryl group, an arylalkyl group, a substituted arylalkyl group, an arylcycloalkyl group, or a substituted arylcycloalkyl group, and the % is based on the total structural units of the hydroxy-functional addition polymer; (3) a cellulose derivative; (4) polyvinylformamide; (5) a cationic epoxy microgel; (6) a polyamine-dialdehyde adduct; (7) a polyetheramine adduct; or any combination thereof.

[0080] As used herein, the term "addition polymer" refers to a polymerization product comprising, at least in part, the residues of unsaturated monomers.

[0081] An addition polymer comprising a polymeric dispersant and a polymerization product of a second-stage ethylenically unsaturated monomer composition. The second-stage ethylenically unsaturated monomer composition comprises a second-stage hydroxyl-functional (meth)acrylamide monomer and / or Second stage hydroxyl functional (meth)acrylate monomer. The organic resin component may include an addition polymer comprising the polymerization product of a polymeric dispersant and a second-stage ethylenically unsaturated monomer composition comprising a second-stage hydroxyl-functional (meth)acrylamide monomer and / or a second-stage hydroxyl-functional (meth)acrylate monomer.

[0082] According to the present disclosure, the electrodeposited coating and / or the electrodepositable coating composition may comprise an addition polymer.

[0083] The addition polymer may include an acrylic polymer comprising a polymer dispersant and a second-stage ethylenically unsaturated monomer composition comprising a polymer product of an aqueous dispersion. As used herein, the term "acrylic polymer" refers to a polymer product comprising at least in part a residue of a (meth) acrylic acid monomer. The polymer product may be formed by a two-stage polymerization process, wherein the polymer dispersant is polymerized during the first stage, and the second-stage ethylenically unsaturated monomer composition is added to the aqueous dispersion of the polymer dispersant and polymerized in the presence of the polymer dispersant participating in the polymerization to form an acrylic polymer during the second stage. Non-limiting examples of acrylic polymers comprising a polymer dispersant and a second-stage ethylenically unsaturated monomer composition comprising a polymer product of an aqueous dispersion are described in International Publication No. WO 2018 / 160799 A1, paragraphs

[0013] to

[0055] , the cited portion of which is incorporated herein by reference.

[0084] The addition polymer may alternatively comprise the polymerization product of a polymeric dispersant and a second-stage ethylenically unsaturated monomer composition comprising a second-stage (meth)acrylamide monomer.

[0085] According to the present disclosure, the polymeric dispersant may include any polymeric dispersant having a sufficient salt group content to stably disperse and participate in the subsequent polymerization of the second-stage ethylenically unsaturated monomer composition and provide a resulting addition polymer that is stable in the electrodepositable coating composition. While reference is made to a polymeric dispersant that is polymerized during the first stage, it should be understood that a preformed or commercially available dispersant may be used and that the prior formation of the polymeric dispersant should be considered a first-stage polymerization.

[0086] According to the present disclosure, the polymeric dispersant polymerized during the first stage may include the polymerization product of the first stage ethylenically unsaturated monomer composition.

[0087] The first stage ethylenically unsaturated monomer composition comprises one or more monomers that allow ionic salt groups to be introduced into the polymeric dispersant, so that the polymeric dispersant comprises a polymeric dispersant containing ionic salt groups. For example, the polymeric dispersant may comprise cationic salt groups, so that the polymeric dispersant comprises a polymeric dispersant containing cationic salt groups; or may comprise anionic salt groups, so that the polymeric dispersant comprises a polymeric dispersant containing anionic salt groups. Cationic salt groups can be formed by introducing epoxide functional unsaturated monomers, amino functional unsaturated monomers, or a combination thereof and subsequently neutralizing. For example, the polymeric dispersant can comprise a polymeric dispersant containing cationic salt groups, which comprises the polymerized product of the first stage ethylenically unsaturated monomer composition, which comprises epoxide functional ethylenically unsaturated monomers and / or amino functional ethylenically unsaturated monomers. Anionic salt groups can be formed by introducing acid functional unsaturated monomers and subsequently neutralizing. For example, the polymeric dispersant can include 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.

[0088] The first stage ethylenically unsaturated monomer composition may optionally include an epoxide functional monomer. The epoxide functional monomer allows the epoxide functional group to be introduced into the polymeric dispersant. The epoxide functional group can be converted into a cationic salt group via the epoxide functional group and amine reaction and neutralized with an acid. Examples of suitable epoxide functional monomers include glycidyl acrylate, glycidyl methacrylate, 3,4-epoxycyclohexyl methyl (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 wt % to 50 wt %, such as 5 wt % to 40 wt %, such as 5 wt % to 30 wt %, such as 5 wt % to 25 wt %, such as 5 wt % to 20 wt %, such as 10 wt % to 50 wt %, such as 10 wt % to 40 wt %, such as 10 wt % to 30 wt %, such as 10 wt % to 25 wt %, such as 10 wt % to 20 wt %, such as 20 wt % to 50 wt %, such as 20 wt % to 40 wt %, such as 20 wt % to 30 wt %, such as 20 wt % to 25 wt %.

[0089] The first stage ethylenically unsaturated monomer composition can optionally include amino-functional monomers.Amino-functional monomers allow amino-functional groups to be introduced into polymeric dispersants.Amino-functional groups can be converted into cationic salt groups by neutralization with acid.Amino-functional monomers can include any suitable amino-functional unsaturated monomers, such as, for example, N-alkylaminoalkyl (methyl) acrylate, N,N-(dialkyl) aminoalkyl (methyl) acrylate, aminoalkyl (methyl) acrylate etc. The specific non-limiting examples of suitable amino-functional monomers include 2-aminoethyl (methyl) acrylate, 2-(dimethylamino) ethyl methacrylate (" DMAEMA"), 2-(dimethylamino) ethyl acrylate, 3-(dimethylamino) propyl (methyl) acrylate, 2-(diethylamino) ethyl (methyl) acrylate, 2-(tert-butylamino) ethyl (methyl) acrylate and 2-(diethylamino) ethyl (methyl) acrylate, and combinations thereof. The amino-functional monomer may be present in an amount of 5 wt % to 50 wt %, such as 5 wt % to 40 wt %, such as 5 wt % to 30 wt %, such as 5 wt % to 25 wt %, such as 5 wt % to 20 wt %, such as 10 wt % to 50 wt %, such as 10 wt % to 40 wt %, such as 10 wt % to 30 wt %, such as 10 wt % to 25 wt %, such as 10 wt % to 20 wt %, such as 20 wt % to 50 wt %, such as 20 wt % to 40 wt %, such as 20 wt % to 30 wt %, such as 20 wt % to 25 wt %.

[0090] The first stage ethylenically unsaturated monomer composition can optionally comprise acid-functional ethylenically unsaturated monomer.Acid-functional monomer allows by neutralizing with alkali anionic salt group is introduced in the polymeric dispersant.Acid-functional ethylenically unsaturated monomer can comprise phosphoric acid or carboxylic acid functional ethylenically unsaturated monomer, as (methyl) acrylic acid.Gross weight based on the first stage ethylenically unsaturated monomer composition, acid-functional monomer can be present in the first stage ethylenically unsaturated monomer composition with the amount of 5 % by weight to 50 % by weight: such as 5 % by weight to 40 % by weight, such as 5 % by weight to 30 % by weight, such as 5 % by weight to 25 % by weight, such as 5 % by weight to 20 % by weight, such as 10 % by weight to 50 % by weight, such as 10 % by weight to 40 % by weight, such as 10 % by weight to 30 % by weight, such as 10 % by weight to 25 % by weight, such as 10 % by weight to 20 % by weight, such as 20 % by weight to 50 % by weight, such as 20 % by weight to 40 % by weight, such as 20 % by weight to 30 % by weight, such as 20 % by weight to 25 % by weight.

[0091] The first stage ethylenically unsaturated monomer composition may optionally further comprise at least one of the following: C1-C 18 Alkyl (meth)acrylates; first stage hydroxyl functional (meth)acrylates; vinyl aromatic compounds; and / or monomers containing two or more ethylenically unsaturated groups per molecule.

[0092] The first stage ethylenically unsaturated monomer composition may optionally further comprise a monoolefin aliphatic compound such as a C1-C 18 Alkyl (meth) acrylate. Suitable (meth) acrylic acid C1-C 18 Examples of alkyl esters 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. Based on the total weight of the first-stage ethylenically unsaturated monomer composition, C1-C 18Alkyl (meth) acrylate can be present in the first stage ethylenically unsaturated monomer composition with an amount of 30 wt % to 90 wt %, such as 30 wt % to 80 wt %, such as 30 wt % to 70 wt %, such as 30 wt % to 60 wt %, such as 40 wt % to 90 wt %, such as 40 wt % to 80 wt %, such as 40 wt % to 70 wt %, such as 40 wt % to 60 wt %, such as 50 wt % to 90 wt %, such as 50 wt % to 80 wt %, such as 50 wt % to 70 wt %, such as 50 wt % to 60 wt %, such as 60 wt % to 90 wt %, such as 60 wt % to 80 wt %, such as 60 wt % to 70 wt %, such as 70 wt % to 90 wt %, such as 70 wt % to 80 wt %. As used herein, " (meth) acrylate " and similar terms encompass both acrylate and methacrylate.

[0093] The ethylenically unsaturated monomer composition optionally may 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). The hydroxyl-functional (meth)acrylate may include hydroxyalkyl (meth)acrylates, such as, for example, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate, and the like, and combinations thereof. The hydroxyl functional (meth)acrylate may be present in the first stage ethylenically unsaturated monomer composition in an amount of 1 wt % to 40 wt %, such as 1 wt % to 30 wt %, such as 1 wt % to 25 wt %, such as 1 wt % to 15 wt %, such as 5 wt % to 40 wt %, such as 5 wt % to 30 wt %, such as 5 wt % to 25 wt %, such as 5 wt % to 15 wt %, such as 10 wt % to 40 wt %, such as 10 wt % to 30 wt %, such as 10 wt % to 25 wt %, such as 10 wt % to 15 wt %, based on the total weight of the first stage ethylenically unsaturated monomer composition.

[0094] The first stage ethylenically unsaturated monomer composition may comprise a vinyl aromatic compound. Non-limiting examples of suitable vinyl aromatic compounds include styrene, α-methylstyrene, α-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 wt % to 40 wt %, such as 0.5 wt % to 30 wt %, such as 0.5 wt % to 20 wt %, such as 0.5 wt % to 15 wt %, such as 0.5 wt % to 10 wt %, such as 1 wt % to 40 wt %, such as 1 wt % to 30 wt %, such as 1 wt % to 20 wt %, such as 1 wt % to 15 wt %, such as 1 wt % to 10 wt %, such as 5 wt % to 40 wt %, such as 5 wt % to 30 wt %, such as 5 wt % to 20 wt %, such as 5 wt % to 15 wt %, such as 5 wt % to 10 wt %, such as 10 wt % to 40 wt %, such as 10 wt % to 30 wt %, such as 10 wt % to 20 wt %, such as 10 wt % to 15 wt %.

[0095] The first stage ethylenically unsaturated monomer composition optionally can comprise that each molecule comprises the monomer of two or more ethylenically unsaturated groups.The monomer that each molecule comprises two or more ethylenically unsaturated groups can comprise that each molecule has the monomer of two ethylenically unsaturated groups.The example that each molecule has the suitable monomer of two ethylenically unsaturated groups comprises ethylene glycol dimethacrylate, allyl methacrylate, hexanediol diacrylate, methacrylic anhydride, tetraethylene glycol diacrylate and / or tripropylene glycol diacrylate.The example that each molecule has the monomer of three or more ethylenically unsaturated groups comprises the ethoxylated trimethylolpropane triacrylate with 0 to 20 ethoxy units, [ethoxylation] trimethylolpropane trimethacrylate with 0 to 20 ethoxy units, di-pentaerythritol triacrylate, pentaerythritol tetraacrylate and / or di-pentaerythritol pentaacrylate. Based on the total weight of the first-stage ethylenically unsaturated monomer composition, the monomer containing two or more ethylenically unsaturated groups per molecule can be present in the first-stage ethylenically unsaturated monomer composition in an amount of 0.1% to 10% by weight, such as 0.1% to 5% by weight, such as 0.1% to 3% by weight, such as 1% to 10% by weight, such as 1% to 5% by weight, such as 1% to 3% by weight, such as 3% to 10% by weight, such as 3% to 5% by weight, such as 5% to 10% by weight. The use of monomers containing two or more ethylenically unsaturated groups per molecule in the first-stage ethylenically unsaturated monomer composition can produce a polymeric dispersant containing ethylenically unsaturated groups. Therefore, the polymeric dispersant can contain ethylenically unsaturated groups.

[0096] The first stage ethylenically unsaturated monomer composition may comprise a first stage (meth)acrylamide monomer. As used herein, the term "first stage" with respect to monomers such as (meth)acrylamide monomers is intended to refer to the monomers used during the polymerization of the polymeric dispersant, and the resulting polymeric dispersant comprises its residue. As used herein, the term "(meth)acrylamide" and similar terms encompass both acrylamide and methacrylamide. The first stage (meth)acrylamide monomer may comprise 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 Alkyl (meth) acrylamide monomers, hydroxyl functional (meth) acrylamide monomers, etc.

[0097] The first stage (meth)acrylamide monomer of the first stage ethylenically unsaturated monomer composition may optionally include C1-C 18 Alkyl (meth) acrylamide monomer. Suitable C1-C 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, tert-butyl (meth) acrylamide, and the like. Based on the total weight of the first-stage ethylenically unsaturated monomer composition, C1-C 18 The alkyl (meth) acrylamide monomer may be present in the first stage ethylenically unsaturated monomer composition in an amount of 30 wt % to 90 wt %, such as 30 wt % to 80 wt %, such as 30 wt % to 70 wt %, such as 30 wt % to 60 wt %, such as 40 wt % to 90 wt %, such as 40 wt % to 80 wt %, such as 40 wt % to 70 wt %, such as 40 wt % to 60 wt %, such as 50 wt % to 90 wt %, such as 50 wt % to 80 wt %, such as 50 wt % to 70 wt %, such as 50 wt % to 60 wt %, such as 60 wt % to 90 wt %, such as 60 wt % to 80 wt %, such as 60 wt % to 70 wt %, such as 70 wt % to 90 wt %, such as 70 wt % to 80 wt %.

[0098] 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 acrylamide and methacrylamide having hydroxyl functionality (i.e., containing at least one hydroxyl functional group in the molecule). The first-stage hydroxyl-functional (meth)acrylamide monomer may include hydroxyalkyl (meth)acrylamides, such as, for example, hydroxymethyl (meth)acrylamide, hydroxyethyl (meth)acrylamide, hydroxypropyl (meth)acrylamide, 2-hydroxypropyl (meth)acrylamide, hydroxybutyl (meth)acrylamide, hydroxypentyl (meth)acrylamide, and the like, and combinations thereof. The first stage hydroxyl functional (meth)acrylamide monomer may be present in the first stage ethylenically unsaturated monomer composition in an amount of 1 wt % to 40 wt %, such as 1 wt % to 30 wt %, such as 1 wt % to 25 wt %, such as 1 wt % to 15 wt %, such as 5 wt % to 40 wt %, such as 5 wt % to 30 wt %, such as 5 wt % to 25 wt %, such as 5 wt % to 15 wt %, such as 10 wt % to 40 wt %, such as 10 wt % to 30 wt %, such as 10 wt % to 25 wt %, such as 10 wt % to 15 wt %, based on the total weight of the first stage ethylenically unsaturated monomer composition.

[0099] Polymer dispersants can be prepared in organic solutions by techniques well known in the art. For example, polymer dispersants can be prepared by conventional free radical initiated solution polymerization techniques, wherein the first stage ethylenically unsaturated monomer composition is dissolved in a solvent or solvent mixture and polymerized in the presence of a free radical initiator. Examples of suitable solvents that can be used for organic solution polymerization include alcohols such as ethanol, tert-butyl alcohol and tert-amyl alcohol, tert-butyl alcohol and tert-amyl alcohol; ketones such as acetone, methyl ethyl ketone; and ethers such as dimethyl ether of ethylene glycol. Examples of suitable free radical initiators include free radical initiators that are soluble in a mixture of monomers, such as azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), azobis-(α,γ-dimethylvaleronitrile), tert-butyl perbenzoate, tert-butyl peracetate, benzoyl peroxide, and di-tert-butyl peroxide. Based on the gross weight of the first stage ethylenically unsaturated monomer composition, the free radical initiator can be present in an amount of 0.01 wt % to 6 wt %, such as 1.0 wt % to 4.0 wt %, such as 2.0 wt % to 3.5 wt %. In an example, the solvent can be first heated to reflux, and the mixture of the first stage ethylenically unsaturated monomer composition and the free radical initiator can be slowly added to the reflux solvent. Based on the gross weight of the first stage ethylenically unsaturated monomer composition, the reaction mixture can be maintained at the polymerization temperature to reduce the free monomer content to less than 1.0 wt %, such as less than 0.5 wt %.

[0100] Chain transfer agents can be used in the synthesis of polymeric dispersants, such as those that are soluble in the monomer mixture. Suitable non-limiting examples of such chain transfer agents include: alkyl mercaptans, for example tert-dodecyl mercaptan; ketones, such as methyl ethyl ketone; and chlorinated hydrocarbons, such as chloroform.

[0101] The polymeric dispersant may have a z-average molecular weight (M) of 200,000 g / mol to 2,000,000 g / mol, such as 200,000 g / mol to 1,200,000 g / mol, such as 200,000 g / mol to 900,000 g / mol, such as 250,000 g / mol to 2,000,000 g / mol, such as 250,000 g / mol to 1,200,000 g / mol, such as 250,000 g / mol to 900,000 g / mol, such as 300,000 to 2,000,000 g / mol, such as 300,000 g / mol to 1,200,000 g / mol, such as 300,000 g / mol to 900,000 g / mol. z ).

[0102] According to the present disclosure, the polymer 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, such as 150,000 g / mol to 300,000 g / mol, such as 175,000 g / mol to 750,000 g / mol, such as 175,000 g / mol to 400,000 g / mol, such as 175,000 g / mol to 300,000 g / mol, such as 200,000 g / mol to 750,000 g / mol, such as 200,000 g / mol to 400,000 g / mol, such as 200,000 g / mol to 300,000 g / mol.

[0103] Ionic groups in polymeric dispersants can be formed by at least partially neutralizing basic or acidic groups present in the polymeric dispersant with an acid or base, respectively. Ionic groups in polymer molecules can be charge-neutralized by counterions. The ionic groups and charge-neutralizing counterions can together form salt groups, such that the polymeric dispersant can include polymeric dispersants containing ionic salt groups.

[0104] Thus, the polymeric dispersant can be at least partially neutralized before or during dispersion in a dispersion medium comprising water, for example, by treatment with an acid to form a water-dispersible cationic salt group-containing polymeric dispersant. 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, which impart a positive charge. The polymeric dispersant can be neutralized to a degree of at least 50%, such as at least 70%, of the total theoretical neutralization equivalents. As used herein, "total theoretical neutralization equivalents" refers to the percentage of the stoichiometric amount of acid to the total amount of basic groups, such as amino groups, theoretically present on the polymer. As discussed above, amines can be introduced into the cationic polymeric dispersant by reaction of the amine with epoxide functional groups present in the polymeric dispersant. The dispersing step can be accomplished by combining the neutralized or partially neutralized cationic salt group-containing polymeric dispersant with the dispersion medium of the dispersed phase. Neutralization and dispersion can also be accomplished in a single step by combining the polymeric dispersant and the dispersion medium. The polymer dispersant (or its salt) may be added to the dispersion medium, or the dispersion medium may be added to the polymer dispersant (or its salt). The pH of the dispersion may be in the range of 5 to 9.

[0105] The polymeric dispersant containing cationic salt groups may contain sufficient cationic salt group content to stabilize the subsequent polymerization of the second stage ethylenically unsaturated monomer composition (described below) and provide a stable resulting addition polymer in a cationically electrodeposited coating composition. In addition, the polymeric dispersant containing cationic salt groups may have sufficient cationic salt group content so that when used together with other film-forming resins in a cationically electrodeposited coating composition, the composition will be deposited on a substrate as a coating when subjected to electrodeposition conditions. The polymeric dispersant containing cationic salt groups may contain, for example, 0.1 to 5.0 milliequivalents, such as 0.3 to 1.1 milliequivalents of cationic salt groups per gram of the polymeric dispersant containing cationic salt groups.

[0106] According to the present disclosure, the polymer dispersant can be at least partially neutralized before or during dispersion in a dispersion medium comprising water, for example, by treating with an alkali to form a water-dispersible polymer dispersant containing anionic salt groups. As used herein, the term "polymer dispersant containing anionic salt groups" refers to anionic polymer dispersants containing at least partially neutralized anionic functional groups such as carboxylic acid groups and phosphoric acid groups that impart a negative charge. Non-limiting examples of suitable bases are amines, such as, for example, tertiary amines. The polymer dispersant can be neutralized to at least 50% of the total theoretical neutralization equivalents, or in some cases at least 70%, or in other cases 100% or more. The step of dispersing can be accomplished by combining the neutralized or partially neutralized polymer dispersant containing anionic salt groups with the dispersion medium of the dispersed phase. Neutralization and dispersion can be accomplished in one step by combining the polymer dispersant and the dispersion medium. The polymer dispersant (or its salt) can be added to the dispersion medium, or the dispersion medium can be added to the polymer dispersant (or its salt). The pH of the dispersion can be in the range of 5 to 9.

[0107] The polymeric dispersant containing anionic salt groups may contain sufficient anionic salt group content to stabilize the subsequent polymerization of the second-stage ethylenically unsaturated monomer composition (described below) and provide a stable resulting addition polymer in an anionic electrodepositable coating composition. In addition, the polymeric dispersant containing anionic salt groups may have sufficient anionic salt group content so that when used together with other film-forming resins in an anionic electrodepositable coating composition, the composition will be deposited as a coating on a substrate when subjected to anionic electrodeposition conditions. The polymeric dispersant containing anionic salt groups may contain 0.1 to 5.0 milliequivalents, such as 0.3 to 1.1 milliequivalents of anionic salt groups per gram of the polymeric dispersant containing anionic salt groups.

[0108] According to the present disclosure, the second-stage ethylenically unsaturated monomer composition comprises, consists essentially of, or consists of: a monomer comprising three or more ethylenically unsaturated groups per molecule and at least one other monomer, the other monomer comprising C1-C 18 The second-stage ethylenically unsaturated monomer composition may be substantially free of diene monomer, or in some cases, completely free of diene monomer. As used herein, when referring to the second-stage ethylenically unsaturated monomer composition as being "substantially free" of diene monomer, it is meant that the diene monomer is present in the monomer composition (if any) in an amount of less than 10 wt %, such as less than 5 wt %, less than 2 wt %, or in some cases less than 1 wt % or 0.1 wt %, based on the total weight of the second-stage ethylenically unsaturated monomer composition.

[0109] Non-limiting examples of monomers containing three or more ethylenically unsaturated groups per molecule include 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 having three or more sites of unsaturation is used in an amount of 0.1 to 10 wt %, such as 0.1 to 5 wt %, based on the total weight of the second-stage ethylenically unsaturated monomer composition.

[0110] The second-stage ethylenically unsaturated monomer composition may comprise C1-C2 in an amount of 20 wt % to 80 wt %, such as 20 wt % to 60 wt %, based on the total weight of the second-stage ethylenically unsaturated monomer composition. 18 Alkyl (meth)acrylate (if any).

[0111] The second-stage ethylenically unsaturated monomer composition may comprise the hydroxyl functional (meth)acrylate, if any, in an amount of 5 to 20 wt%, such as 5 to 15 wt%, based on the total weight of the second-stage ethylenically unsaturated monomer composition.

[0112] The second-stage ethylenically unsaturated monomer composition may comprise the vinyl aromatic compound, if any, in an amount from 20 to 80 weight percent, such as from 20 to 60 weight percent, based on the total weight of the second-stage ethylenically unsaturated monomer composition.

[0113] According to the present disclosure, the second-stage ethylenically unsaturated monomer composition comprises, consists essentially of, or consists of one or more second-stage (meth)acrylamide monomers. As used herein, the term "second stage" with respect to monomers such as (meth)acrylamide monomers is intended to refer to the monomers used in the second polymerization step of an addition polymer that is polymerized in the presence of a preformed polymeric dispersant, and the resulting addition polymer comprises residues thereof. The (meth)acrylamide monomers can include any suitable (meth)acrylamide monomer, such as, for example, (meth)acrylamide, a substituted or unsubstituted monoalkyl (meth)acrylamide, or a substituted or unsubstituted dialkyl (meth)acrylamide. Non-limiting examples include (meth)acrylamide, C1-C 18 Alkyl (meth) acrylamide, hydroxyl functional (meth) acrylamide, etc.

[0114] The second-stage ethylenically unsaturated monomer composition can comprise, consist essentially of, or consist 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 wt % to 100 wt %, such as 20 wt % to 99 wt %, such as 20 wt % to 90 wt %, such as 20 wt % to 80 wt %, such as 20 wt % to 70 wt %, such as 20 wt % to 60 wt %, such as 20 wt % to 50 wt %, such as 30 wt % to 100 wt %, such as 30 wt % to 99 wt %, such as 30 wt % to 90 wt %, such as 30 wt % to 80 wt %, such as 30 wt % to 70 wt %, such as 30 wt % to 60 wt %, such as 30 wt % to 50 wt %, such as 40 wt % to 100 wt %, such as 40 wt % to 99 wt %, such as 40 wt % to 90 wt %, such as 40 wt % to 80 wt %, such as 40 wt % to 70 wt %, such as 40 wt % to 60 wt %, such as 40 wt % to 50 wt %. % by weight, such as 50 wt % to 100 wt %, such as 50 wt % to 99 wt %, such as 50 wt % to 90 wt %, such as 50 wt % to 80 wt %, such as 50 wt % to 70 wt %, such as 50 wt % to 60 wt %, such as 60 wt % to 100 wt %, such as 60 wt % to 99 wt %, such as 60 wt % to 90 wt %, such as 60 wt % to 80 wt %, such as 60 wt % to 70 wt %, such as 70 wt % to 100 wt % , such as 70 wt % to 99 wt %, such as 70 wt % to 90 wt %, such as 70 wt % to 80 wt %, such as 80 wt % to 100 wt %, such as 80 wt % to 99 wt %, such as 80 wt % to 90 wt %, such as 90 wt % to 100 wt %, such as 90 wt % to 99 wt %, such as 95 wt % to 100 wt %, such as 95 wt % to 99 wt %, such as 95 wt % to 100 wt %, such as 95 wt % to 99 wt %.

[0115] The second stage ethylenically unsaturated monomer composition may comprise, consist essentially of, or consist 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 a C1-C9 hydroxyalkyl (meth)acrylamide, such as a C1-C6 hydroxyalkyl (meth)acrylamide, such as a C1-C5 hydroxyalkyl (meth)acrylamide, such as, for example, one or more of hydroxymethyl (meth)acrylamide, hydroxyethyl (meth)acrylamide, hydroxypropyl (meth)acrylamide, 2-hydroxypropyl (meth)acrylamide, hydroxybutyl (meth)acrylamide, hydroxypentyl (meth)acrylamide, or any combination thereof.

[0116] The second stage hydroxyl functional (meth)acrylamide monomer may be present in the second stage ethylenically unsaturated monomer composition in an amount of 20 wt % to 100 wt %, such as 20 wt % to 99 wt %, such as 20 wt % to 90 wt %, such as 20 wt % to 80 wt %, such as 20 wt % to 70 wt %, such as 20 wt % to 60 wt %, such as 20 wt % to 50 wt %, such as 30 wt % to 100 wt %, such as 30 wt % to 99 wt %, such as 30 wt % to 90 wt %, such as 30 wt % to 80 wt %, such as 30 wt % to 70 wt %, such as 30 wt % to 60 wt %, such as 30 wt % to 50 wt %, such as 40 wt % to 100 wt %, such as 40 wt % to 99 wt %, such as 40 wt % to 90 wt %, such as 40 wt % to 80 wt %, such as 40 wt % to 70 wt %, such as 40 wt % to 60 wt %, % to 50 wt %, such as 50 wt % to 100 wt %, such as 50 wt % to 99 wt %, such as 50 wt % to 90 wt %, such as 50 wt % to 80 wt %, such as 50 wt % to 70 wt %, such as 50 wt % to 60 wt %, such as 60 wt % to 100 wt %, such as 60 wt % to 99 wt %, such as 60 wt % to 90 wt %, such as 60 wt % to 80 wt %, such as 60 wt % to 70 wt %, such as 70 wt % to 100 wt %. wt %, such as 70 wt % to 99 wt %, such as 70 wt % to 90 wt %, such as 70 wt % to 80 wt %, such as 80 wt % to 100 wt %, such as 80 wt % to 99 wt %, such as 80 wt % to 90 wt %, such as 90 wt % to 100 wt %, such as 90 wt % to 99 wt %, such as 95 wt % to 100 wt %, such as 95 wt % to 99 wt %, such as 95 wt % to 100 wt %, such as 95 wt % to 99 wt %.

[0117] The second stage ethylenically unsaturated monomer composition may optionally include other ethylenically unsaturated monomers. Other ethylenically unsaturated monomers may include any ethylenically unsaturated monomers known in the art. Examples of other ethylenically unsaturated monomers that can be used for the second stage ethylenically unsaturated monomer composition include, but are not limited to, the monomers described above for the preparation of the polymeric dispersant, as well as di(meth)acrylates and poly(ethylene glycol) (meth)acrylates. Such monomers may be present, if any, in an amount of 1 wt % to 80 wt %, such as 1 wt % to 70 wt %, such as 1 wt % to 60 wt %, such as 1 wt % to 50 wt %, such as 1 wt % to 40 wt %, such as 1 wt % to 30 wt %, such as 1 wt % to 20 wt %, such as 1 wt % to 10 wt %, such as 1 wt % to 5 wt %, such as 5 wt % to 80 wt %, such as 5 wt % to 70 wt %, such as 5 wt % to 60 wt %, such as 5 wt % to 50 wt %, such as 5 wt % to 40 wt %, such as 5 wt % to 30 wt %, such as 5 wt % to 20 wt %, such as 5 wt % to 10 wt %. % by weight, such as 10 wt % to 80 wt %, such as 10 wt % to 70 wt %, such as 10 wt % to 60 wt %, such as 10 wt % to 50 wt %, such as 10 wt % to 40 wt %, such as 10 wt % to 30 wt %, such as 10 wt % to 20 wt %, such as 20 wt % to 80 wt %, such as 20 wt % to 70 wt %, such as 20 wt % to 60 wt %, such as 20 wt % to 50 wt %, such as 20 wt % to 40 wt %, such as 20 wt % to 30 wt %, such as 30 wt % to 80 wt %, such as 30 wt % to 70 wt %, such as 30 wt % to 60 wt %, such as 30 wt % to 50 wt %, such as 30 wt % to 40 wt %.

[0118] The addition polymer may include a polymerization product comprising 10 to 90 wt % of a residue of a polymeric dispersant, such as 10 to 80 wt %, such as 10 to 70 wt %, such as 10 to 60 wt %, such as 10 to 50 wt %, such as 10 to 40 wt %, such as 10 to 30 wt %, such as 10 to 20 wt %, such as 20 to 90 wt %, such as 20 to 80 wt %, such as 20 to 70 wt %, such as 20 to 60 wt %, such as 20 to 50 wt %, such as 20 to 40 wt %, such as 20 to 30 wt %, such as 30 to 90 wt %, such as 30 to 80 wt %, such as 30 to 90 wt %. % to 70 wt %, such as 30 wt % to 60 wt %, such as 30 wt % to 50 wt %, such as 30 wt % to 40 wt %, such as 40 wt % to 90 wt %, such as 40 wt % to 80 wt %, such as 40 wt % to 70 wt %, such as 40 wt % to 60 wt %, such as 40 wt % to 50 wt %, such as 50 wt % to 90 wt %, such as 50 wt % to 80 wt %, such as 50 wt % to 70 wt %, such as 50 wt % to 60 wt %, such as 60 wt % to 90 wt %, such as 60 wt % to 80 wt %, such as 60 wt % to 70 wt %, such as 70 wt % to 90 wt %, such as 70 wt % to 80 wt %, such as 80 wt % to 90 wt %, the weight percentages being based on the total weight of the addition polymer.

[0119] The addition polymer may include a polymerization product comprising 10 to 90 weight % of the residue of the second stage ethylenically unsaturated monomer composition, such as 10 to 80 weight %, such as 10 to 70 weight %, such as 10 to 60 weight %, such as 10 to 50 weight %, such as 10 to 40 weight %, such as 10 to 30 weight %, such as 10 to 20 weight %, such as 20 to 90 weight %, such as 20 to 80 weight %, such as 20 to 70 weight %, such as 20 to 60 weight %, such as 20 to 50 weight %, such as 20 to 40 weight %, such as 20 to 30 weight %, such as 30 to 90 weight %, such as 30 to 80 weight %, such as 30 % to 70 wt%, such as 30 wt% to 60 wt%, such as 30 wt% to 50 wt%, such as 30 wt% to 40 wt%, such as 40 wt% to 90 wt%, such as 40 wt% to 80 wt%, such as 40 wt% to 70 wt%, such as 40 wt% to 60 wt%, such as 40 wt% to 50 wt%, such as 50 wt% to 90 wt%, such as 50 wt% to 80 wt%, such as 50 wt% to 70 wt%, such as 50 wt% to 60 wt%, such as 60 wt% to 90 wt%, such as 60 wt% to 80 wt%, such as 60 wt% to 70 wt%, such as 70 wt% to 90 wt%, such as 70 wt% to 80 wt%, such as 80 wt% to 90 wt%, the weight percentages being based on the total weight of the addition polymer.

[0120] According to the present disclosure, the addition polymer may include a polymerization product of a polymer dispersant and a second-stage ethylenically unsaturated monomer composition, wherein the weight ratio of the second-stage ethylenically unsaturated monomer composition to the polymer dispersant may be 9:1 to 1:9, such as 9:1 to 1:4, such as 9:1 to 3:7, such as 9:1 to 2:3, such as 9:1 to 1:1, such as 9:1 to 3:2, such as 9:1 to 7:3, such as 9:1 to 4:1, such as 4:1 to 1:9, such as 4:1 to 1:4, such as 4:1 to 3:7, such as 4:1 to 2:3, such as 4:1 to 1: :1, such as 4:1 to 3:2, such as 4:1 to 7:3, such as 4:1 to 9:1, such as 7:3 to 1:9, such as 7:3 to 1:4, such as 7:3 to 3:7, such as 7:3 to 2:3, such as 7:3 to 1:1, such as 7:3 to 3:2, such as 7:3 to 4:1, such as 7:3 to 9:1, such as 3:2 to 1:9, such as 3:2 to 1:4, such as 3:2 to 3:7, such as 3:2 to 2:3, such as 3:2 to 1:1, such as 3:2 to 7:3, such as 3:2 to 4:1, such as 3:2 to 9:1, such as 1: 1 to 1:9, such as 1:1 to 1:4, such as 1:1 to 3:7, such as 1:1 to 2:3, such as 1:1 to 3:2, such as 1:1 to 7:3, such as 1:1 to 4:1, such as 1:1 to 9:1, such as 2:3 to 1:9, such as 2:3 to 1:4, such as 2:3 to 3:7, such as 2:3 to 1:1, such as 2:3 to 3:2, such as 9:1 to 7:3, such as 2:3 to 4:1, such as 2:3 to 9:1, such as 3:7 to 1:9, such as 3:7 to 1:4, such as 3:7 to 2:3, such as 3:7 to 1:1, etc. Such as 3:7 to 3:2, such as 3:7 to 7:3, such as 3:7 to 4:1, such as 3:7 to 9:1, such as 1:4 to 1:9, such as 1.4 to 3:7, such as 1.4 to 2:3, such as 1.4 to 1:1, such as 1.4 to 3:2, such as 1.4 to 7:3, such as 1.4 to 4:1, such as 1:4 to 9:1, such as 1:9 to 1:4, such as 1:9 to 3:7, such as 1:9 to 2:3, such as 1:9 to 1:1, such as 1:9 to 3:2, such as 1:9 to 7:3, such as 1:9 to 4:1, such as 1:9 to 9:1.

[0121] The addition polymer may contain active hydrogen functional groups. The active hydrogen functional groups may include hydroxyl groups, thiol groups, primary amine groups and / or secondary amine groups.

[0122] The addition polymer may have a theoretical hydroxyl equivalent weight of 120 g / OH to 310 g / OH, such as 130 g / OH to 275 g / OH, such as 140 g / OH to 200 g / OH, such as 145 g / OH to 160 g / OH.

[0123] The addition polymer may have a theoretical hydroxyl value of 190 to 400 mg KOH / gram of addition polymer, such as 250 to 390 mg KOH / gram of addition polymer, such as 320 to 380 mg KOH / gram of addition polymer, such as 355 to 370 mg KOH / gram of addition polymer. As used herein, the term "theoretical hydroxyl value" generally refers to the number of milligrams of potassium hydroxide required to neutralize the acetic acid absorbed by one gram of a chemical substance containing free hydroxyl groups during acetylation, and is determined herein by theoretical calculation of the number of free hydroxyl groups theoretically present in one gram of addition polymer.

[0124] 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 according to the same procedure as described above.

[0125] 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 following the same procedure as above.

[0126] According to the present disclosure, the addition polymer can be substantially free, essentially free, or completely free of silicon. As used herein, "silicon" refers to elemental silicon or any silicon-containing compound, such as an organosilicon compound including an alkoxysilane. As used herein, an addition polymer is "substantially free" of silicon if silicon is present in the addition polymer in an amount of less than 2 weight percent, based on the total weight of the addition polymer. As used herein, an addition polymer is "essentially free" of silicon if silicon is present in the addition polymer in an amount of less than 1 weight percent, based on the total weight of the addition polymer. As used herein, an addition polymer is "completely free" of silicon if silicon is not present in the addition polymer, i.e., 0 weight percent.

[0127] According to the present disclosure, addition polymers can be formed by a two-stage polymerization process. The first stage of the two-stage polymerization process includes forming a polymer dispersant from the first stage ethylenically unsaturated monomer composition as described above. The second stage of the two-stage polymerization process includes forming an addition polymer, which includes the polymerized product of the polymer dispersant formed during the first stage and the second stage ethylenically unsaturated monomer composition as described above. The second stage of the polymerization process can include: (a) dispersing the second stage ethylenically unsaturated monomer composition and a free radical initiator in a dispersion medium comprising water in the presence of an at least partially neutralized polymer dispersant to form an aqueous dispersion; and (b) subjecting the aqueous dispersion to emulsion polymerization conditions (e.g., by heating in the presence of a free radical initiator) to polymerize the components to form an aqueous dispersion comprising the formed addition polymer. The time and temperature of the polymerization can depend on each other, the selected ingredients, and in some cases the scale of the reaction. For example, the polymerization can be carried out at 40°C to 100°C for 2 to 20 hours.

[0128] The free radical initiator used for the polymerization of the polymeric dispersant and the second-stage ethylenically unsaturated monomer composition can be selected from any free radical initiator used in aqueous addition polymerization techniques, including redox couple initiators, peroxides, hydroperoxides, peroxydicarbonates, azo compounds, and the like. The free radical initiator can be present in an amount of 0.01 to 5 weight percent, such as 0.05 to 2.0 weight percent, and such as 0.1 to 1.5 weight percent, 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, for example, tert-dodecyl mercaptan, 2-mercaptoethanol, isooctyl mercaptopropionate, n-octyl mercaptan, or 3-mercaptoacetic acid, can be used for the polymerization of the polymeric dispersant and the second-stage ethylenically unsaturated monomer composition. Other chain transfer agents, such as ketones, for example, methyl ethyl ketone, and chlorocarbons such as chloroform, can be used. If present, the amount of the chain transfer agent can be 0.1 to 6.0 weight percent, based on the weight of the second-stage ethylenically unsaturated monomer composition. Relatively high molecular weight polyfunctional mercaptans may replace all or part of the chain transfer agent. For example, the molecular weight of these molecules may range from about 94 to 1,000 g / mol or higher. The functionality may range from about 2 to about 4. If present, these polyfunctional mercaptans may be present in an amount of 0.1 wt % to 6.0 wt % based on the weight of the second-stage ethylenically unsaturated monomer composition.

[0129] Based on the total weight of the aqueous dispersion, water may be present in the aqueous dispersion in an amount of 40 to 90 wt %, such as 40 to 75 wt %, such as 40 to 60 wt %, such as 50 to 90 wt %, such as 50 to 75 wt %, such as 50 to 60 wt %, such as 60 to 90 wt %, such as 60 to 75 wt %, such as 75 to 90 wt %. The addition polymer may be added to the other components of the electrodepositable coating composition as an aqueous dispersion of the addition polymer.

[0130] In addition to water, the dispersion medium may further include an organic cosolvent. The organic cosolvent may be at least partially soluble in water. Examples of such organic solvents include oxygenated organic solvents, such as monoalkyl ethers of ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol containing 1 to 10 carbon atoms in the alkyl group, such as the monoethyl ether and monobutyl ether of these glycols. Other examples of at least partially water-miscible solvents include alcohols, such as ethanol, isopropyl alcohol, butanol, and diacetone alcohol. If used, the organic cosolvent may be present in an amount of less than 10% by weight, such as less than 5% by weight, based on the total weight of the dispersion medium.

[0131] The addition polymer may be present in the electrodepositable coating composition in an amount of 0.01 wt % to 5 wt %, such as 0.01 wt % to 3 wt %, such as 0.01 wt % to 2 wt %, such as 0.01 wt % to 1.5 wt %, such as 0.01 wt % to 1 wt %, such as 0.01 wt % to 0.75 wt %, such as 0.1 wt % to 5 wt %, such as 0.1 wt % to 3 wt %, such as 0.1 wt % to 2 wt %, such as 0.1 wt % to 1.5 wt %, such as 0.1 wt % to 1 wt %, such as 0.1 wt % to 0.75 wt %, Such as 0.3 wt% to 5 wt%, such as 0.3 wt% to 3 wt%, such as 0.3 wt% to 2 wt%, such as 0.3 wt% to 1.5 wt%, such as 0.3 wt% to 1 wt%, such as 0.3 wt% to 0.75 wt%, such as 0.5 wt% to 5 wt%, such as 0.5 wt% to 3 wt%, such as 0.5 wt% to 2 wt%, such as 0.5 wt% to 1.5 wt%, such as 0.5 wt% to 1 wt%, such as 0.5 wt% to 0.75 wt%, such as 1 wt% to 5 wt%, such as 1 wt% to 3 wt%, such as 1 wt% to 2 wt%, such as 1 wt% to 1.5 wt%.

[0132] Hydroxy-functional addition polymers As described above, the organic resin component may include a hydroxy-functional addition polymer comprising structural units, at least 70% of which comprise Formula VIII:

[0133] —[—C(R 1 )2—C(R 1 )(OH)—]—(VIII),

[0134] Each R 1 The % is independently one of hydrogen, an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an alkylcycloalkyl group, a substituted alkylcycloalkyl group, a cycloalkylalkyl group, a substituted cycloalkylalkyl group, an aryl group, a substituted aryl group, an alkylaryl group, a substituted alkylaryl group, a cycloalkylaryl group, a substituted cycloalkylaryl group, an arylalkyl group, a substituted arylalkyl group, an arylcycloalkyl group, or a substituted arylcycloalkyl group, and the % is based on the total structural units of the hydroxy-functional addition polymer. Although the above addition polymer may contain a hydroxyl functional group, it is different from a hydroxy-functional addition polymer.

[0135] Non-limiting examples of suitable alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl and 2-ethylhexyl.

[0136] Non-limiting examples of suitable cycloalkyl groups include cyclobutyl, cyclopentyl and cyclohexyl.

[0137] Non-limiting examples of suitable alkylcycloalkyl groups include methylenecyclohexane, ethylenecyclohexane, and propane-1,3-diylcyclohexane.

[0138] Non-limiting examples of suitable cycloalkylalkyl groups include 2-, 3-, and 4-methyl-, -ethyl-, -propyl-, and -butylcyclohex-1-yl.

[0139] Non-limiting examples of suitable aryl groups include phenyl, naphthyl, and biphenyl.

[0140] Non-limiting examples of suitable alkylaryl groups include benzyl-[sic], ethylene-, and propane-1,3-diyl-benzene.

[0141] Non-limiting examples of suitable cycloalkylaryl groups include 2-, 3- and 4-phenylcyclohex-1-yl.

[0142] Non-limiting examples of suitable arylalkyl groups include 2-, 3-, and 4-methyl-, ethyl-, propyl-, and butylphenyl-1-yl.

[0143] Non-limiting examples of suitable arylcycloalkyls include 2-, 3- and 4-cyclohexylphenyl-1-yl.

[0144] The above group R 1Electron-withdrawing or electron-donating atoms or organic groups can be used for this purpose.

[0145] Examples of suitable substituents include halogen atoms such as chlorine or fluorine, nitrile groups, nitro groups (partially or fully halogenated, such as chlorinated and / or fluorinated), alkyl, cycloalkyl, alkylcycloalkyl, cycloalkylalkyl, aryl, alkylaryl, cycloalkylaryl, arylalkyl and arylcycloalkyl groups, including those exemplified above, especially tert-butyl; aryloxy, alkoxy and cycloalkyloxy groups, especially phenoxy, naphthoxy, methoxy, ethoxy, propoxy, butoxy or cyclohexyloxy; arylthio, alkylthio and cycloalkyl groups, especially phenoxy, naphthoxy, methoxy, ethoxy, propoxy, butoxy or cyclohexyloxy; arylthio, alkylthio and cycloalkyl groups, including those exemplified above, especially tert-butyl; Alkylthio, in particular phenylthio, naphthylthio, methylthio, ethylthio, propylthio, butylthio or cyclohexylthio; hydroxyl groups; and / or primary, secondary and / or tertiary amino groups, in particular amino, N-methylamino, N-ethylamino, N-propylamino, N-phenylamino, N-cyclohexylamino, N,N-dimethylamino, N,N-diethylamino, N,N-dipropylamino, N,N-diphenylamino, N,N-dicyclohexylamino, N-cyclohexyl-N-methylamino or N-ethyl-N-methylamino.

[0146] R 1 may comprise, consist essentially of, or consist of hydrogen. For example, R 1 Hydrogen may be contained in at least 80% of the structural units according to formula VIII, such as at least 90% of the structural units, such as at least 92% of the structural units, such as at least 95% of the structural units, such as 100% of the structural units.

[0147] The hydroxy-functional addition polymer can include at least 70%, such as at least 80%, such as at least 85%, such as at least 90% of the structural unit according to formula VIII, and this % is based on the total structural unit of the hydroxy-functional addition polymer. The hydroxy-functional addition polymer can include no more than 100%, such as no more than 95%, such as no more than 92%, such as no more than 90% of the structural unit according to formula VIII, and this % is based on the total structural unit of the hydroxy-functional addition polymer. The hydroxy-functional addition polymer can include the structural unit according to formula VIII in an amount of 70% to 95%, such as 80% to 95%, such as 85% to 95%, such as 90% to 95%, such as 92% to 95%, such as 70% to 92%, such as 80% to 92%, such as 85% to 92%, such as 90% to 92%, such as 70% to 90%, such as 80% to 90%, such as 85% to 90%, and this % is based on the total structural unit of the hydroxy-functional addition polymer.

[0148] According to the present disclosure, the hydroxyl functional addition polymer may optionally further comprise a structural unit comprising a residue of a vinyl ester. The vinyl ester may comprise any suitable vinyl ester. For example, the vinyl ester may be according to the formula C(R1 )2==C(R 1 )(C(O)CH3) represents, wherein each R 1 and independently one of hydrogen, an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an alkylcycloalkyl group, a substituted alkylcycloalkyl group, a cycloalkylalkyl group, a substituted cycloalkylalkyl group, an aryl group, a substituted aryl group, an alkylaryl group, a substituted alkylaryl group, a cycloalkylaryl group, a substituted cycloalkylaryl group, an arylalkyl group, a substituted arylalkyl group, an arylcycloalkyl group, or a substituted arylcycloalkyl group. Non-limiting examples of suitable vinyl esters include vinyl acetate, vinyl formate, or any combination thereof.

[0149] According to the present disclosure, hydroxy-functional addition polymers can be formed by polymerizing vinyl ester monomers to form an intermediate polymer comprising structural units containing residues of vinyl esters, and subsequently hydrolyzing the structural units of the intermediate polymer comprising residues of vinyl esters to form a hydroxy-functional addition polymer. The residues of vinyl esters can comprise 70% to 95%, such as 80% to 95%, such as 85% to 95%, such as 90% to 95%, such as 92% to 95%, such as 70% to 92%, such as 80% to 92%, such as 85% to 92%, such as 90% to 92%, such as 70% to 90%, such as 80% to 90%, such as 85% to 90%, the % being based on the total structural units of the intermediate polymer.

[0150] According to the present disclosure, the hydroxyl-functional addition polymer may have a theoretical hydroxyl equivalent weight of 30 g / OH to 200 g / OH, such as 30 g / OH to 100 g / OH, such as 30 g / OH to 60 g / OH, such as 30 g / OH to 50 g / OH, such as 35 g / OH to 200 g / OH, such as 35 g / OH to 100 g / OH, such as 35 g / OH to 60 g / OH, such as 35 g / OH to 50 g / OH, such as 40 g / OH to 200 g / OH, such as 40 g / OH to 100 g / OH, such as 40 g / OH to 60 g / OH, such as 40 g / OH to 50 g / OH, such as 44 g / OH to 200 g / OH, such as 44 g / OH to 100 g / OH, such as 44 g / OH to 60 g / OH, such as 44 g / OH to 50 g / OH. As used herein, the term "theoretical hydroxyl equivalent weight" refers to the weight of hydroxyl-functional addition polymer resin solids in grams divided by the theoretical equivalent weight of hydroxyl groups present in the hydroxyl-functional addition polymer and can be calculated according to the following formula (a):

[0151] (a)

[0152] According to the present disclosure, the hydroxyl-functional addition polymer may have a theoretical hydroxyl value of 1,000 to 1,300 mg KOH / gram of addition polymer, such as 1,000 to 1,200 mg KOH / gram of addition polymer, such as 1,000 to 1,150 mg KOH / gram of addition polymer, such as 1,100 to 1,300 mg KOH / gram of addition polymer, such as 1,100 to 1,200 mg KOH / gram of addition polymer, such as 1,100 to 1,150 mg KOH / gram of addition polymer, such as 1,150 to 1,300 mg KOH / gram of addition polymer, such as 1,150 to 1,200 mg KOH / gram of addition polymer.

[0153] According to the present disclosure, the hydroxyl functional addition polymer may have a density of 5,000 g / mol to 500,000 g / mol, such as 5,000 g / mol to 300,000 g / mol, such as 5,000 g / mol to 200,000 g / mol, such as 5,000 g / mol to 125,000 g / mol, such as 25,000 g / mol to 500,000 g / mol, such as 25,000 g / mol to 300,000 g / mol, such as 25,000 to 200,000 g / mol, such as 25,000 g / mol to 125,000 g / mol, such as The number average molecular weight (M) is 75,000 g / mol to 500,000 g / mol, such as 75,000 g / mol to 300,000 g / mol, such as 75,000 g / mol to 200,000 g / mol, such as 75,000 g / mol to 125,000 g / mol, such as 100,000 g / mol to 500,000 g / mol, such as 100,000 g / mol to 300,000 g / mol, such as 100,000 g / mol to 200,000 g / mol, such as 100,000 g / mol to 125,000 g / mol. n ), as determined by gel permeation chromatography using polystyrene calibration standards.

[0154] According to the present disclosure, the hydroxyl functional addition polymer may have a density of 5,000 g / mol to 500,000 g / mol, such as 5,000 g / mol to 300,000 g / mol, such as 5,000 g / mol to 200,000 g / mol, such as 5,000 g / mol to 125,000 g / mol, such as 25,000 g / mol to 500,000 g / mol, such as 25,000 g / mol to 300,000 g / mol, such as 25,000 to 200,000 g / mol, such as 25,000 g / mol to 125,000 g / mol, such as 75,000 g / mol to 800,000 g / mol. 500,000 g / mol, such as 75,000 g / mol to 300,000 g / mol, such as 75,000 g / mol to 200,000 g / mol, such as 75,000 g / mol to 125,000 g / mol, such as 100,000 g / mol to 500,000 g / mol, such as 100,000 g / mol to 300,000 g / mol, such as 100,000 g / mol to 200,000 g / mol, such as 100,000 g / mol to 125,000 g / mol, as determined by gel permeation chromatography using polystyrene calibration standards.

[0155] As used herein, unless otherwise indicated, the term "number average molecular weight (M)" refers to n )" and "weight average molecular weight (M w )" means the number average molecular weight (M) as determined by gel permeation chromatography using the following n ) and weight average molecular weight (M w ): A Waters 2695 separation module 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) with 0.05 M lithium bromide (LiBr) as eluent at a flow rate of 0.5 mL / min, and an Asahipak GF-510HQ column were used for separation.

[0156] According to the present disclosure, a solution of 4 wt% of a hydroxyl-functional addition polymer dissolved in water may have a viscosity of 10 cP to 110 cP, such as 10 cP to 90 cP, such as 10 cP to 70 cP, such as 10 cP to 50 cP, such as 10 cP to 40 cP, such as 15 cP to 110 cP, such as 15 cP to 90 cP, such as 15 cP to 70 cP, such as 15 cP to 60 cP, such as 15 cP to 50 cP, such as 15 cP to 40 cP, such as 20 cP to 110 cP, such as 20 cP to 90 cP, such as 20 cP to 70 cP, such as 20 cP to 60 cP, such as 20 cP to 50 cP, such as 20 cP to 40 cP, as measured using a Brookfield synchronous motor rotational viscometer at 20°C.

[0157] According to the present disclosure, the above-mentioned 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 %, such as at least 0.3 wt %, such as at least 0.5 wt %, such as at least 0.75 wt %, such as 1 wt %, based on the total weight of the resin solids of the electrodepositable coating composition. The hydroxyl-functional addition polymer may be present in the electrodepositable coating composition in an amount of no more than 5 wt %, such as no more than 3 wt %, such as no more than 2 wt %, such as no more than 1.5 wt %, such as no more than 1 wt %, such as no more than 0.75 wt %. The hydroxyl-functional addition polymer may be present in the electrodepositable coating composition in an amount of 0.01 wt % to 5 wt %, such as 0.01 wt % to 3 wt %, such as 0.01 wt % to 2 wt %, such as 0.01 wt % to 1.5 wt %, such as 0.01 wt % to 1 wt %, such as 0.01 wt % to 0.75 wt %, such as 0.1 wt % to 5 wt %, such as 0.1 wt % to 3 wt %, such as 0.1 wt % to 2 wt %, such as 0.1 wt % to 1.5 wt %, such as 0.1 wt % to 1 wt %, such as 0.1 wt % to 0.75 wt %. %, such as 0.3 wt% to 5 wt%, such as 0.3 wt% to 3 wt%, such as 0.3 wt% to 2 wt%, such as 0.3 wt% to 1.5 wt%, such as 0.3 wt% to 1 wt%, such as 0.3 wt% to 0.75 wt%, such as 0.5 wt% to 5 wt%, such as 0.5 wt% to 3 wt%, such as 0.5 wt% to 2 wt%, such as 0.5 wt% to 1.5 wt%, such as 0.5 wt% to 1 wt%, such as 0.5 wt% to 0.75 wt%, such as 1 wt% to 5 wt%, such as 1 wt% to 3 wt%, such as 1 wt% to 2 wt%, such as 1 wt% to 1.5 wt%.

[0158] cellulose As mentioned above, the organic resin component can include a water-soluble cellulose derivative. The water-soluble cellulose derivative can include hydroxyethyl cellulose, carboxymethyl cellulose, carboxymethyl hydroxyethyl cellulose, hydroxymethyl cellulose, carboxyethyl cellulose, their salts and their combinations. For example, the water-soluble cellulose derivative can include carboxymethyl cellulose and its salts (CMC). CMC is a cellulose ether in which part of the hydroxyl groups on the anhydroglucose ring is replaced by carboxymethyl groups. The degree of carboxymethyl substitution can vary in the range of 0.4 to 3. Since CMC is a long-chain polymer, its viscosity in aqueous solution depends on its molecular weight, and the molecular weight can vary between 50,000 g / mol and 2,000,000 g / mol based on weight average. Carboxymethyl cellulose can have a weight average molecular weight of at least 50,000, such as at least 100,000, such as at least 200,000, such as 50,000 to 1,000,000, 100,000 to 500,000, such as 200,000 to 300,000 g / mol. The degree of substitution and the viscosity of aqueous solutions can both be determined by ASTM D 1439-03. Molecular weight is usually estimated from the viscosity of a standard CMC solution.

[0159] 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%, such as 0.001 to 10% or 0.05 to 2%, based on the total weight of resin solids.

[0160] Polyvinyl formamide polymer As mentioned above, the organic resin component may include a polyvinyl formamide polymer. The polyvinyl formamide polymer may be unhydrolyzed, partially hydrolyzed, or fully hydrolyzed. Hydrolysis of the formamide groups provides primary amine groups; fully hydrolyzed polyvinyl formamide polymer provides poly(vinylamine). Hydrolyzed polyvinyl formamide polymers are marketed under the trademark Commercially available from BASF, it has different weight average molecular weights (from about 340,000 Daltons to less than 10,000 Daltons) and various degrees of hydrolysis (10%, 30%, and 90%). Unhydrolyzed or hydrolyzed polyvinyl formamide polymers may also contain monomer units other than vinyl amide and vinyl amine monomer units. In one embodiment of such copolymers, vinyl formamide may be copolymerized with vinyl acetate; hydrolysis of the resulting copolymer provides vinyl alcohol monomer units as well as vinyl amine monomer units. In one embodiment, the polyvinyl formamide polymer contains only vinyl amide and vinyl amine monomer units (i.e., the polyvinyl formamide polymer is a homopolymer of vinyl formamide or a homopolymer of at least partially hydrolyzed vinyl formamide).

[0161] The electrodeposition coating composition includes unhydrolyzed or hydrolyzed polyvinyl formamide polymer, typically in an amount less than one weight percent of the coating composition. For example, the electrodeposition coating composition may include at least about 25 ppm by weight of unhydrolyzed or hydrolyzed polyvinyl formamide polymer; in other embodiments, the aqueous electrodeposition coating composition may include at least about 50 ppm by weight of unhydrolyzed or hydrolyzed polyvinyl formamide polymer. For example, the aqueous electrodeposition coating composition may include up to about 1000 ppm by weight of unhydrolyzed or hydrolyzed polyvinyl formamide polymer; in other examples, the electrodeposition coating composition may include up to about 100 ppm by weight of 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 are achieved with an amount of unhydrolyzed or hydrolyzed polyvinyl formamide polymer less than 1000 ppm, based on the weight of the aqueous electrodeposition coating composition.

[0162] Cationic epoxy microgel According to the present disclosure, the organic resin component may include a cationic epoxy microgel. Cationic epoxy microgel refers to a cationic microgel dispersion prepared by first dispersing a reaction mixture of a cationic polyepoxide-amine reaction product and a polyepoxide crosslinker in an aqueous medium. The dispersing step can be accomplished by adding the polyepoxide-amine reaction product (preferably at an elevated temperature of 100°C to 150°C) to a mixture of water and an acid to form a cationic dispersion of the resin in water. Typically, the resulting dispersion will have a solids content of about 20% to 50% by weight and a degree of neutralization of 20% to 100% of the total theoretical neutralization. The acid can be an organic acid, such as formic acid, lactic acid, and acetic acid, or an inorganic acid, such as phosphoric acid and sulfamic acid. In addition, blends of acids, including blends of organic and inorganic acids, can also be used. The degree of neutralization depends on the specific reaction product, and typically only enough acid is added to stabilize the resulting microgel dispersion. The expression "cationic polyepoxide-amine reaction product containing primary and / or secondary amine groups" includes primary amine groups, secondary amine groups and acid salts thereof.

[0163] Polyamine-dialdehyde adduct: According to the present disclosure, the pit control additive may comprise a polyamine-dialdehyde adduct comprising, or in some cases consisting of, or in some cases consisting essentially of, the polymerization product of a polyamine and a dialdehyde. The polyamine and the dialdehyde may be polymerized to form the polymerization product. As used herein, "polyamine" includes compounds containing at least two amino groups, and these amino groups may include primary or secondary amino groups. As used herein, a "primary amino group" is a derivative of ammonia in which one of the hydrogen atoms has been replaced by an alkyl group or an aryl group, while a "secondary amino group" is a derivative of ammonia in which both hydrogen atoms have been replaced by an alkyl group or an aryl group. As used herein, "alkyl" refers to a hydrocarbon chain that may be straight or branched and may contain one or more hydrocarbon rings that are not aromatic. As used herein, "aryl" refers to a substituted or unsubstituted hydrocarbon having a delocalized conjugated π-system in which double bonds and single bonds alternate between the carbon atoms to form one or more coplanar hydrocarbon rings.

[0164] According to the present disclosure, the polyamine can include a cationic amine functionalized resin, a polyetheramine, or a combination thereof. The cationic amine functionalized resin can be derived from a polyepoxide. For example, the cationic amine functionalized resin can be prepared by reacting the polyepoxide with a polyhydroxyl-containing material selected from a material containing alcoholic hydroxyl groups and a material containing phenolic hydroxyl groups to extend the chain or build up the molecular weight of the polyepoxide. Other hydroxyl-containing materials that can comprise the cationic amine functionalized resin include adducts of materials containing phenolic hydroxyl groups and alkylene oxides. The reaction product can then be reacted with a cationic salt group-forming agent to produce the cationic amine functionalized resin.

[0165] According to the present disclosure, polyamines may also include polyetheramines, which may be characterized by propylene oxide, ethylene oxide, or mixed propylene oxide and ethylene oxide repeating units in their respective structures, such as, for example, one of the Jeffamine series of products (commercially available from Huntsman Corporation). Examples of such polyetheramines include aminated propoxylated pentaerythritol (such as Jeffamine XTJ-616) and those compounds represented by formula (IX) to formula (IX) to (XI).

[0166] According to formula (IX) of the present disclosure, the polyetheramine may include or represent:

[0167]

[0168] Wherein y=0-39, x+z=1-68.

[0169] Suitable polyetheramines represented by formula (IX) include, but are not limited to, amine-terminated polyethylene glycols, such as Huntsman's Jeffamine ED series, such as 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, such as Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, and Jeffamine D-4000.

[0170] According to formula (X) of the present disclosure, the polyetheramine may include or represent:

[0171]

[0172] wherein each p is independently 2 or 3.

[0173] Suitable polyetheramines represented by formula (X) include, but are not limited to, amine-terminated polyethylene glycol-based diamines, such as Huntsman's Jeffamine EDR series, such as Jeffamine EDR-148 and Jeffamine EDR-176.

[0174] According to formula (XI) of the present disclosure, the polyetheramine may include or represent:

[0175]

[0176] Wherein R is H or C2H5, m=0 or 1, a+b+c=5-85.

[0177] Suitable polyetheramines represented by formula (XI) include, but are not limited to, amine terminated propoxylated trimethylolpropane or glycerol, such as Huntsman's Jeffamine T series, such as Jeffamine T-403, Jeffamine T-3000, and Jeffamine T-5000.

[0178] The average molecular weight of the polyamine (M z ) can be 5,000 g / mol to 300,000 g / mol, such as 7,000 g / mol to 100,000 g / mol, such as 10,000 g / mol to 15,000 g / mol. As used herein, the term "z-average molecular weight (M)" refers to the molecular weight of the polymer. z )" means the average molecular weight (M) as determined by gel permeation chromatography using the following z): A Waters 2695 separation module 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) with lithium bromide (LiBr) as eluent at a flow rate of 0.5 mL / min, and an Asahipak GF-510HQ column were used for separation.

[0179] The amine equivalent weight of the polyamine can be 200 g / amine to 5,000 g / amine, such as 400 g / amine to 2,000 g / amine, such as 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.

[0180] As described above, according to the present disclosure, polyamines can be polymerized with dialdehydes to form polyamine-dialdehyde adducts. Each dialdehyde molecule can contain two aldehyde functional groups. As used herein, "aldehyde functional group" includes the structure R-CHO, wherein the carbon atom of the carbonyl group 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.

[0181] According to the present disclosure, the polymerization of polyamines and dialdehydes to form polyamine-dialdehyde adducts can be carried out in an aqueous medium at a pH of less than 7, such as less than 6.5, and can 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 can be carried out in an aqueous medium at a pH of 2 to 7, such as 5 to 6.5.

[0182] According to the present disclosure, the polyalkylene oxide polymer 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 recognize that there are inherent limitations in molecular weight measurements for high molecular weight compounds (such as compounds with a molecular weight exceeding 900,000 g / mol). Therefore, although the theoretical z-average molecular weight (Mz) of the polyamine-dialdehyde adduct is z ) is expected to increase as the dialdehyde to polyamine ratio approaches 1 (i.e., the dialdehyde to polyamine ratio <1), but due to limitations in the measurement standards, the measured molecular weight may not reflect this. This result is expected, not because the adducts do not have increased molecular weight at higher stoichiometric ratios, but rather because the analytical methods according to the present invention make it difficult to measure the molecular weight of such high-molecular-weight compounds. Specifically, because GPC is a size-exclusion chromatography method, higher molecular weight polymers elute from the column faster than lower molecular weight polymers. Once most polymers exceed a certain molecular weight, the polymer molecules elute from the column too quickly to accurately determine their molecular weight.

[0183] As discussed in more detail below, the polyamine-dialdehyde adduct can function in the electrodepositable coating composition as a primary vehicle, as an additive added to the electrodepositable coating composition as a pre-blended component of the resin blend, or as a combination of a primary vehicle and an additive.

[0184] As described above, according to the present disclosure, the polyamine-dialdehyde adduct can be used as a primary carrier in an electrodepositable coating composition. In such cases, 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% by weight, such as 75% to 85% by weight, based on the total amount of resin blend solids.

[0185] According to the present disclosure, polyamine-dialdehyde adducts can be used as primary carriers. According to the present disclosure, the stoichiometric ratio of the aldehyde functional groups of the dialdehyde compound to the primary and / or secondary amino functional groups from the polyamine can be 2:1 to 20:1, such as 3:1 to 15:1, such as 4:1 to 14:1.

[0186] According to the present disclosure, the polyamine-dialdehyde adduct can also be used as a primary carrier in an electrodepositable coating composition. In this case, according to the present disclosure, the polyamine-dialdehyde adduct can be present in the electrodepositable coating composition in an amount of 0.2 wt % to 20 wt %, such as 0.5 wt % to 15 wt %, such as 0.75 wt % to 10 wt %, such as 1 wt % to 4 wt %, based on the total amount of resin blend solids.

[0187] According to the present disclosure, polyamine-dialdehyde adducts can be used as additives. In such cases, the stoichiometric ratio of the aldehyde functional groups from the dialdehyde compound to the 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, such as 5:10 to 7:10. As the stoichiometric ratio of the aldehyde functional groups to the amino functional groups increases, assuming the number of amino groups per polyamine molecule remains constant, the molecular weight of the resulting polyamine-dialdehyde adduct increases accordingly.

[0188] Polyetheramine adduct: According to the present disclosure, the electrodepositable coating composition may further include a polyetheramine adduct, which includes an ungelled ionic reaction product prepared from reactants, the ungelled ionic reaction product including: (a) an epoxy functional material or a reaction product prepared from reactants, the reactants including: (1) a polyol; and (2) an epoxy functional material; and (b) a polyetheramine.

[0189] Examples of suitable epoxy-functional materials that can be used to form the ungelled ionic reaction product contain at least one epoxy group in the molecule, such as di- or polyglycidyl ethers of polyols, such as polyglycidyl ethers of bisphenol A. Suitable epoxy-functional materials can have an epoxy equivalent weight in the range of about 90 to about 2000, as measured by titration with perchloric acid using methyl violet as an indicator. The epoxy-functional material can include about 10% to 40% by weight, such as 15% to 35% by weight, of the epoxy-functional material, based on the total weight of the epoxy-functional polyester, which is combined or reacted with the polyether described above to form the epoxy-functional polyester.

[0190] Examples of suitable polyols that can be used to form the ungelled ionic reaction product include resorcinol, dihydroxybenzenes, aliphatic, alicyclic or aromatic hydroxy compounds such as ethylene glycol, propylene glycol, bisphenol A, dihydroxycyclohexane, dimethylolcyclohexane or combinations thereof. The polyol can 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 polyester reaction product.

[0191] 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 characterized by propylene oxide, ethylene oxide, or mixed propylene oxide and ethylene oxide repeating units in their respective structures, such as, for example, one of the Jeffamine series of products (commercially available from Huntsman Corporation). Examples of such polyetheramines include aminated propoxylated pentaerythritol (such as Jeffamine XTJ-616) and those represented by formulas (IX) to (XI).

[0192] Additional examples of polyetheramine adducts are those described in US Pat. Nos. 4,420,574 and 4,423,166, which are incorporated herein by reference.

[0193] The polyetheramine adduct may have a polyalkylene oxide content of at least 50 wt %, such as polyethylene oxide content, polypropylene oxide content, polybutylene oxide content, etc., based on the total weight of the polyetheramine adduct, such as at least 60 wt %, such as at least 70 wt %, such as at least 80 wt %, such as at least 90 wt %.

[0194] 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, such as at least 10,000 g / mol, such as at least 30,000 g / mol, such as at least 50,000 g / mol, such as at least 75,000 g / mol, such as 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 not more than 500,000 g / mol, such as not more than 400,000 g / mol, such as not more than 300,000 g / mol, such as not more than 250,000 g / mol, such as not more than 200,000 g / mol, such as not more than 150,000 g / mol, such as not more than 100,000 g / mol, such as not more than 50,000 g / mol, such as not more than 25,000 g / mol, such as not more than 10,000 g / mol, such as not more than 8,000 g / mol. The polyetheramine adduct may have a molecular weight of 1,000 to 500,000 g / mol, such as 1,000 to 400,000 g / mol, such as 1,000 to 300,000 g / mol, such as 1,000 to 250,000 g / mol, such as 1,000 to 200,000 g / mol, such as 1,000 to 150,000 g / mol, such as 1,000 to 100,000 g / mol, such as 1,000 to 50,000 g / mol, such as 1,000 to 25,000 g / mol, such as 1,000 to 10,000 g / mol, such as 1,000 to 8,000 g / mol, such as 3,000 to 500,000 g / mol, such as 3,000 to 400,000 g / mol, such as 3,000 to 300,000 g / mol, such as 3,000 to 250,000 g / mol, such as 3,000 0 to 200,000 g / mol, such as 3,000 to 150,000 g / mol, such as 3,000 to 100,000 g / mol, such as 3,000 to 50,000 g / mol, such as 3,000 to 25,000 g / mol, such as 3,000 to 10,000 g / mol, such as 3,000 to 8,000 g / mol, such as 10,000 to 500,000 g / mol, such as 1 0,000 to 400,000 g / mol, such as 10,000 to 300,000 g / mol, such as 10,000 to 250,000 g / mol, such as 10,000 to 200,000 g / mol, such as 10,000 to 150,000 g / mol, such as 10,000 to 100,000 g / mol, such as 10,000 to 50,000 g / mol, such as 10,000 to 25,000 g / mol, such as 30,000 to 500,000 g / mol, such as 30,000 to 400,000 g / mol, such as 30,000 to 300,000 g / mol, such as 30,000 to 250,000 g / mol, such as 30,000 to 200,000 g / mol, such as 30,000 to 150,000 g / mol, such as 30,000 to 100,000 g / mol, such as 30,000 to 50,000 g / mol, such as 50,000 to 500,000 g / mol, such as 50,000 to 400,000 g / mol, such as 50,000 to 300,000 g / mol, such as 50,000 to 250,000 g / mol, such as 50,000 to 200,000 g / mol, such as 50,000 to 150,000 g / mol, such as 50,000 to 100,000 g / mol, such as 75,000 to 500,000 g / mol, such as 75,000 to 400,000 g / mol, such as 75, 000 to 300,000 g / mol, such as 75,000 to 250,000 g / mol, such as 75,000 to 200,000 g / mol, such as 75,000 to 150,000 g / mol, such as 75,000 to 100,000 g / mol, such as 100,000 to 500,000 g / mol, such as 100,000 to 400,000 g / mol, such as 100,000 to 300,000 g / mol, such as 100,000 to 250,000 g / mol mol, such as 100,000 to 200,000 g / mol, such as 100,000 to 150,000 g / mol, such as 125,000 to 500,000 g / mol, such as 125,000 to 400,000 g / mol, such as 125,000 to 300,000 g / mol, such as 125,000 to 250,000 g / mol, such as 125,000 to 200,000 g / mol, such as a weight average molecular weight of 125,000 to 150,000 g / mol.

[0195] The polyetheramine adduct may be present in the electrodeposition coating and / or the electrodepositionable coating composition in an amount of 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 electrodepositionable binder. The polyetheramine adduct may be present in the electrodeposition coating and / or the electrodepositionable coating composition in an amount of no more than 35 wt %, such as no more than 30 wt %, such as no more than 25 wt %, such as no more than 20 wt %, such as no more than 15 wt %, such as no more than 10 wt %, such as no more than 5 wt %, based on the total weight of the electrodepositionable binder. The polyetheramine adduct may be present in the electrodeposition coating and / or electrodepositable coating composition in an amount of 3 wt % to 35 wt %, such as 3 wt % to 30 wt %, such as 3 wt % to 25 wt %, such as 3 wt % to 20 wt %, such as 3 wt % to 15 wt %, such as 3 wt % to 10 wt %, such as 3 wt % to 5 wt %, such as 5 wt % to 35 wt %, such as 5 wt % to 30 wt %, such as 5 wt % to 25 wt %, such as 5 wt % to 20 wt %, such as 5 wt % to 15 wt %, such as 5 wt % to 10 wt %, % to 10 wt%, such as 10 wt% to 35 wt%, such as 10 wt% to 30 wt%, such as 10 wt% to 25 wt%, such as 10 wt% to 20 wt%, such as 10 wt% to 15 wt%, such as 15 wt% to 35 wt%, such as 15 wt% to 30 wt%, such as 15 wt% to 25 wt%, such as 15 wt% to 20 wt%, such as 20 wt% to 35 wt%, such as 20 wt% to 30 wt%, such as 20 wt% to 25 wt%, such as 25 wt% to 35 wt%, such as 25 wt% to 30 wt%.

[0196] Additional components of electrodeposited coatings and / or electrodepositable coating compositions

[0197] In addition to the components described above, the electrodeposited coating and / or electrodepositable coating composition may optionally comprise one or more additional components.

[0198] The electrodeposited coating and / or the electrodepositable composition may optionally include a corrosion inhibitor. Any suitable corrosion inhibitor may be used. For example, the corrosion inhibitor may include an inhibitor comprising yttrium, lanthanum, cerium, calcium, azole, or any combination thereof.

[0199] Non-limiting examples of suitable azoles include benzotriazole, 5-methylbenzotriazole, 2-aminothiazole, and salts thereof.

[0200] Based on the total weight of the electrodeposition coating and / or the total solid weight of the electrodeposited coating composition, the corrosion inhibitor may be present in the electrodeposition coating and / or the electrodeposited coating composition, if any, in an amount of at least 0.001 wt %, such as at least 5 wt %. Based on the total weight of the electrodeposition coating and / or the total solid weight of the electrodeposited coating composition, the corrosion inhibitor may be present in the electrodeposited coating and / or the electrodeposited coating composition, if any, in an amount of no more than 25 wt %, such as no more than 15 wt %, such as no more than 10 wt %. Based on the total weight of the electrodeposition coating and / or the total solid weight of the electrodeposited coating composition, the corrosion inhibitor may be present in the electrodeposited coating composition, if any, in an amount of no more than 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 %.

[0201] Alternatively, the electrodeposited coating and / or electrodepositable coating composition may be substantially free, essentially free, or completely free of corrosion inhibitors.

[0202] According to the present disclosure, the electrodeposition coating and / or electrodepositable coating composition may contain other optional ingredients, such as various additives (if desired), such as fillers, plasticizers, antioxidants, biocides, UV light absorbers and stabilizers, hindered amine light stabilizers, defoamers, fungicides, dispersing aids, flow control agents, surfactants, wetting agents or combinations thereof. Alternatively, the electrodeposition coating and / or electrodepositable coating composition may be completely free of any optional ingredients, i.e., the optional ingredients are not present in the electrodeposition coating and / or electrodepositable coating composition. The other additives mentioned above may be present in the electrodeposition coating and / or electrodepositable coating composition in an amount of 0.01 wt % to 3 wt %, based on the total weight of the resin solids of the electrodeposition coating and / or electrodepositable coating composition.

[0203] The electrodeposited coating and / or electrodepositable coating composition optionally may 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.

[0204] The flame retardant pigment may include inorganic pigments, minerals, or a combination thereof.

[0205] As used herein, the term "inorganic" refers to materials that do not contain carbon atoms.

[0206] Non-limiting examples of inorganic pigments or minerals include metal hydroxides such as aluminum hydroxide, aluminum oxide, or hydrates thereof, magnesium hydroxide, zinc compounds such as zinc borate or zinc hydroxystannate, metal borates, titanium dioxide, barium sulfate, geopolymers such as alkali metal aluminum silicates, calcite, hydromagnesite, red phosphorus, boron compounds such as borates, organic layered silicates, wollastonite, carbonates such as calcium carbonate and 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, corundum, diamond, silver, zinc, copper, gold, carbonyl iron, copper, zinc, aluminum, clay, color pigments such as cadmium yellow, cadmium red, chrome yellow, or combinations thereof.

[0207] The flame retardant pigment can be reported in at least one dimension as 0.01 micron to 100 microns, such as 0.01 micron to 50 microns, such as 0.01 micron to 40 microns, such as 0.01 micron to 25 microns, such as 2 microns to 100 microns, such as 2 microns to 50 microns, such as 2 microns to 40 microns, such as 2 microns to 25 microns, such as 10 microns to 100 microns, such as 10 microns to 50 microns, such as 10 microns to 40 microns, such as 10 microns to 25 microns. Suitable methods for measuring average particle size include, for example, measurements using an instrument such as a Quanta 250 FEG SEM or equivalent.

[0208] 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 no more than 0.17: 1, such as no more than 0.15: 1, such as no more than 0.12: 1, such as no more than 0.1: 1, such as no more than 0.05: 1. The flame retardant pigment may be present in the flame retardant electrodepositable coating composition in the following flame retardant pigment to binder (P:B) ratio: 0.01:1 to less than 0.2:1, such as 0.01:1 to 0.17:1, such as 0.01:1 to 0.15:1, such as 0.01:1 to 0.12:1, such as 0.01:1 to 0.1:1, such as 0.01:1 to 0.05:1, such as 0.05 to less than 0.2:1, such as 0.05:1 to 0.17:1, such as 0.05:1 to 0.15:1, such as 0.01:1 to 0.12:1. 0.5:1 to 0.12:1, such as 0.05:1 to 0.1:1, such as 0.1:1 to less than 0.2:1, such as 0.1:1 to 0.17:1, such as 0.1:1 to 0.15:1, such as 0.1:1 to 0.12:1, such as 0.12:1 to less than 0.2:1, such as 0.12:1 to 0.17:1, such as 0.12:1 to 0.15:1, such as 0.15:1 to less than 0.2:1, such as 0.15:1 to 0.17:1, such as 0.17:1 to less than 0.2:1.

[0209] The electrodeposited 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 besides hydrogen, oxygen and / or nitrogen, such as, for example, halogens, sulfur, phosphorus, silicon, etc., but excluding melamine derivatives that include such atoms.

[0210] Hybrid organic-inorganic materials can contribute to the flame retardancy of coatings deposited from the electrodepositable coating composition.

[0211] Non-limiting examples of hybrid organic-inorganic materials include organic halogen compounds, phosphorus-containing resins (such as organic phosphorus compounds), organic silicone resins, sulfur-containing resins, nanogels, or combinations thereof.

[0212] Suitable examples of organohalogen compounds include organochlorines such as chlorobridgeic acid derivatives and chlorinated paraffins; organobromines such as decabromodiphenyl ether (decaBDE), decabromodiphenyl ethane (a substitute for decaBDE), polymeric brominated compounds such as brominated polystyrene, brominated carbonate oligomers (BCO), brominated epoxy resin oligomers (BEO), tetrabromophthalic anhydride, tetrabromobisphenol A (TBBPA), and hexabromocyclododecane (HBCD). Such halogenated materials can be used in combination with synergists to enhance their efficiency. Other suitable examples include antimony trioxide, antimony pentoxide, and sodium antimonate.

[0213] Suitable examples of organophosphorus compounds include triphenyl phosphate (TPP), resorcinol bis(diphenyl phosphate) (RDP), bisphenol A diphenyl phosphate (BADP), and tricresyl phosphate (TCP); phosphonates such as dimethyl methylphosphonate (DMMP); and phosphinates such as aluminum diethylphosphite.

[0214] Hybrid organic-inorganic materials can also include compounds containing both phosphorus and halogens. These compounds include tris(2,3-dibromopropyl)phosphate (tris bromide) and chlorinated organic phosphates such as tris(1,3-dichloro-2-propyl)phosphate (tris chloride or TDCPP) and tetrakis(2-chloroethyl)dichloroisopentyl diphosphate (V6).

[0215] The hybrid organic-inorganic material may also include ammonium polyphosphate.

[0216] The electrodeposited coating and / or electrodepositable coating composition may optionally further comprise an organic flame retardant additive.

[0217] As used herein, the term "organic flame retardant additive" refers to an organic compound that contributes to the flame retardancy of a coating, and 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 derivative contains atoms other than carbon, hydrogen, oxygen, and nitrogen.

[0218] Organic flame retardant additives can include organic compounds such as carboxylic acids, dicarboxylic acids, melamine and their derivatives (including those comprising phosphates), phenolic resins, and organic nitrogen compounds. For example, the organic compound can include carboxylic acids, dicarboxylic acids, melamine, melamine polyphosphate, melamine zinc polyphosphate, melamine aluminum polyphosphate, melamine-based hindered amine light stabilizers, phenolic resins, expanded graphite, organic nitrogen compounds, or combinations thereof.

[0219] The electrodeposited coating and / or electrodepositable coating composition may be substantially free, essentially free, or completely free of montmorillonite.

[0220] According to the present disclosure, the coating composition that can be electrodeposited can include water and / or one or more organic solvents. Based on the gross weight of the coating composition that can be electrodeposited, water can, for example, exist in an amount of 40 wt % to 90 wt % (such as 50 wt % to 75 wt %). The example of a suitable organic solvent comprises an oxygen-containing organic solvent, such as the monoalkyl ether containing 1 to 10 carbon atoms in the alkyl group of ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol, such as the monoethyl ether and monobutyl ether of these glycols. Other examples of water-miscible solvents at least in part comprise alcohols, such as ethanol, isopropanol, butanol and diacetone alcohol. If used, then based on the gross weight of the coating composition that can be electrodeposited, the organic solvent can generally exist in an amount less than 10 wt % (such as less than 5 wt %). The coating composition that can be electrodeposited can specifically be provided in the form of a dispersion (such as an aqueous dispersion).

[0221] According to the present disclosure, the total solids content of the electrodepositable coating composition may be at least 1% by weight, such as at least 5% by weight, and may be no more than 50% by weight, such as no more than 40% by weight, such as no more than 20% by weight, based on the total weight of the electrodepositable coating composition. The total solids content of the electrodepositable coating composition may be from 1% to 50% by weight, such as from 5% to 40% by weight, such as from 5% to 20% by weight, based on the total weight of the electrodepositable coating composition. As used herein, "total solids" refers to the non-volatile content of the electrodepositable coating composition, i.e., materials that will not volatilize when heated to 110° C. for 15 minutes.

[0222] substrate

[0223] According to the present disclosure, the coating composition that can be electrodeposited can be applied electrophoretically to a conductive substrate. The coating composition that can be electrodeposited can be electrophoretically deposited on any conductive substrate. Suitable substrates include metal substrates, metal alloy substrates and / or metallized substrates, such as nickel-plated plastics. Additionally, the substrate can comprise a non-metallic conductive material, including a composite material, such as a material that, for example, comprises carbon fiber or conductive carbon. According to the present disclosure, the metal or metal alloy can include cold-rolled steel, hot-rolled steel, stainless steel, steel coated with zinc metal, a zinc compound or a zinc alloy, such as electrogalvanized steel, hot-dip galvanized steel, alloyed hot-dip galvanized steel and steel coated with a zinc alloy. Aluminum alloys of the 2XXX, 3XXX, 4XXX, 5XXX, 6XXX or 7XXX series and composite aluminum alloys and cast aluminum alloys of the A356 series can also be used as substrates. Magnesium alloys of the AZ31B, AZ91C, AM60B or EV31A series can also be used as substrates. The substrate used in the present disclosure can also include titanium and / or titanium alloys. Other suitable non-ferrous metals include copper and magnesium and alloys of these materials. Suitable metal substrates for use in the present disclosure include metal substrates commonly used in vehicle body assemblies (such as, but not limited to, doors, body panels, trunk lids, roof panels, hoods, roof and / or stringers, rivets, landing gear components and / or skins used on aircraft), vehicle frames, vehicle parts, motorcycles, wheels, industrial structures and components, such as household appliances including washers, dryers, refrigerators, stoves, dishwashers, etc., agricultural equipment, lawn and garden equipment, air conditioning units, heat pump units, lawn furniture, and other articles of manufacture. As used herein, "vehicle" or variations thereof include, but are not limited to, civil, commercial, and military aircraft and / or land vehicles, such as automobiles, motorcycles, trucks, tanks, and / or armored cars or trucks. The metal substrate can also be in the form of, for example, metal sheets or prefabricated parts. It should also be understood that the substrate can be pretreated with a pretreatment solution comprising a zinc phosphate pretreatment solution, such as, for example, those described in U.S. Pat. Nos. 4,793,867 and 5,588,989, or a zirconium-containing pretreatment solution, such as, for example, those described in U.S. Pat. Nos. 7,749,368 and 8,673,091.

[0224] The substrate can be a multi-metal article. As used herein, the term "multi-metal article" refers to (1) an article having at least one surface comprising a first metal and at least one surface comprising a second metal different from the first metal, (2) a first article having at least one surface comprising a first metal and a second article having at least one surface comprising a second metal different from the first metal, or (3) both (1) and (2). The substrate can include surfaces or portions of different substrate materials that are adjacent or joined together, such as, for example, a plated component.

[0225] Coating method, coating and coated substrate

[0226] As is known to those skilled in the art, the electrodepositable coating composition can be electrophoretically applied to a conductive substrate and at least partially cured using application conditions, time, and temperature.

[0227] The cationic electrodepositable coating composition of the present disclosure can be deposited on a conductive substrate by contacting the composition with a conductive cathode and a conductive anode, wherein the surface to be coated is 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.

[0228] The anionic electrodepositable coating composition of the present disclosure can be deposited on a conductive substrate by contacting the composition with a conductive cathode and a conductive anode, wherein the surface to be coated is 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.

[0229] The voltage applied in the electrophoretic application of the electrodepositable coating compositions of the present disclosure can vary and can be, for example, as low as one volt to as high as several thousand volts, such as between 50 and 500 volts. For example, the current density can be between 0.5 and 15 amps per square foot and tends to decrease during electrodeposition, indicating the formation of an insulating film.

[0230] The substrate of the electrodeposited coating at least partially coated with the coating composition deposited by the present invention can be heated to a temperature and 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 so that at least a portion of the reactive groups of the coating composition components are cured or crosslinked to form a coating. Typically, the substrate can 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), such as 300°F to 360°F (149°C to 180°C). For the purposes of this disclosure, all that is necessary is that the time is sufficient to achieve the curing of the coating on the substrate. For example, the curing time can be in the range of 10 minutes to 60 minutes, such as 20 minutes to 40 minutes. The thickness of the resulting cured electrodeposited coating is not limited and can optionally be in the range of 15 microns to 50 microns.

[0231] The present disclosure also relates to a method for coating a substrate (such as any of the conductive substrates mentioned above). According to the present disclosure, such a method may include electrophoretically applying an electrodepositable coating composition as described above to at least a portion of the substrate and curing the coating composition to form an at least partially cured coating on the substrate. According to the present disclosure, the method may include (a) electrophoretically depositing the 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) directly applying one or more pigmented coating compositions and / or one or more non-pigmented coating compositions to the at least partially cured electrodeposited coating to form a topcoat layer on at least a portion of the at least partially cured electrodeposited coating; and (d) heating the coated substrate of step (c) to a temperature and for a time sufficient to cure the topcoat layer.

[0232] The electrodepositable coating composition of the present disclosure may comprise a multilayer coating system. The coating deposited by the composition of the present invention may have one or more additional coatings deposited below and / or above the layer. 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 in the present disclosure may be deposited above at least a portion of the pretreatment layer; one or more additional coatings may be applied to at least a portion of the electrodeposited coating. 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 coatings, the additional coatings including primers, basecoats, color coatings, monocoats, clearcoats, and / or topcoats. Suitable additional coatings include any of those known in the art, and each independently may be waterborne, solvent-based, in the form of solid particulates (i.e., powder coating compositions), or in the form of powder slurries. The additional coatings may be cured independently of each other, or optionally applied "wet on wet" and cured simultaneously. As used herein, "wet-on-wet" refers to a process in which a coating layer (eg, a clear coat) is applied over a substantially uncured, different coating layer (eg, a color coat), and both coating layers are cured simultaneously.

[0233] The coating system may optionally include in any coating layer or layers one or a mixture of two or more colorants and / or fillers known to those skilled in the art in any amount sufficient to impart the desired characteristic, visual and / or color effect.

[0234] The present disclosure further relates to electrodepositable coatings formed by at least partially curing a film from the electrodepositable coating compositions described herein.

[0235] The present disclosure also relates to a coated substrate comprising a coating deposited from the electrodepositable coating composition described above.

[0236] The coated substrate can be coated by the methods described herein.

[0237] The coated conductive substrate optionally may not include or may be free of a pretreatment layer positioned between the substrate and the electrodeposited coating.

[0238] The coated conductive substrate optionally may not include any intervening coatings between the substrate and the electrodeposited coating.

[0239] In addition, the topcoat layer can be applied directly to the coating that can be electrodeposited. In other words, the substrate can lack a primer layer. For example, the primer layer can be applied directly to at least a portion of the electrodeposited coating.

[0240] The electrodeposition coating may have a thickness of less than 55 g / m 2 A water vapor transmission rate of less than 50 g / m / day as measured by the WATER VAPOR TRANSMITTANCE TEST METHOD 2 / day, such as less than 45g / m 2 / day, such as less than 40g / m 2 / sky.

[0241] The electrodeposited coating may have an edge coverage greater than 20%, 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% as measured by the EDGE COVERAGE TEST METHOD.

[0242] As used herein, unless otherwise defined herein, the term "substantially free" means that the ingredient is present in an amount of 1 wt % or less based on the total weight of the electrodeposited coating and / or the total solids weight of the electrodepositable coating composition.

[0243] As used herein, unless otherwise defined herein, the term "substantially free" means that the ingredient is present in an amount of 0.1 wt % or less based on the total weight of the electrodeposited coating and / or the total solids weight of the electrodepositable coating composition.

[0244] As used herein, unless otherwise defined herein, the term "completely free" means that the ingredient is not present in the coating composition, i.e., 0.00 wt %, based on the total weight of the electrodeposited coating and / or the total solids weight of the electrodepositable coating composition.

[0245] For the purpose of this detailed description, it should be understood that except for the cases explicitly stated to the contrary, the present disclosure can take alternative variations and step orders. In addition, except in any operating examples, or when otherwise indicated, all figures expressing the amount of the ingredients used in this specification and claims should be understood to be modified by the term "about" in all cases. Therefore, unless otherwise indicated, the numerical parameters set forth in the following description and the appended claims are approximate values ​​that can be changed according to the desired properties to be obtained by the present disclosure. At least, and not attempting to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be interpreted according to the number of reported significant figures and by applying common rounding techniques.

[0246] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values ​​set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0247] Furthermore, it should be understood that any numerical range recited herein is intended to include all subranges subsumed therein. For example, a range of "1 to 10" is intended to include (and include) all subranges between the recited minimum value of 1 and the recited maximum value of 10, i.e., having a minimum value equal to or greater than 1 and a maximum value equal to or less than 10.

[0248] As used herein, "comprising," "containing," and similar terms are understood in the context of this application to be synonymous with "comprising" and are therefore open-ended and do not exclude the presence of additional undescribed or unrecited elements, materials, ingredients, or method steps. As used herein, "consisting of" is understood in the context of this application to exclude the presence of any unspecified elements, ingredients, or method steps. As used herein, "consisting essentially of" is understood in the context of this application to include the specified elements, materials, ingredients, or method steps "as well as those elements, materials, ingredients, or method steps that do not materially affect the basic and novel characteristics of what is described."

[0249] In this application, unless otherwise specifically stated, the use of the singular includes the plural, and the plural encompasses the singular. For example, although reference is made herein to "a" film-forming polymer containing an ionic salt group, "a" hydroxyl-functional addition polymer, "a" monomer, "a" film-forming polymer containing an ionic salt group, and "a" blocked polyisocyanate curing agent, combinations (i.e., multiples) of these components may be used. In addition, in this application, unless otherwise specifically stated, the use of "or" means "and / or," even though "and / or" may be explicitly used in some cases.

[0250] While specific aspects of the present disclosure have been described in detail, those skilled in the art will appreciate that various modifications and alternatives to those details can be developed based on the overall teachings of the present disclosure. Therefore, the particular arrangements disclosed are intended to be illustrative only and not limiting of the scope of the present disclosure, which is to be given by the full scope of the appended claims and any and all equivalent forms thereof.

[0251] The following examples illustrate the present disclosure, which, however, should not be considered to limit the disclosure to its details.Unless otherwise indicated, all parts and percentages in the following examples and throughout the specification are by weight.

[0252] Examples

[0253] Preparation of resin systems for Examples 1-9

[0254] Preparation of Crosslinker I: A blocked polyisocyanate crosslinker suitable for electrodepositable coating resins was prepared in the following manner. Components 2-6 listed in Table 1 below were mixed in a flask set to total reflux with stirring under nitrogen. The mixture was heated to a temperature of 110°C and component 1 was added dropwise such that the temperature rose due to the exothermic reaction and remained below 110°C. After the addition of component 1 was complete, component 7 was added to the heated reaction mixture. A temperature of 110°C was established in the reaction mixture and the reaction mixture was maintained at that temperature until no residual isocyanate was detected by IR spectroscopy. Components 8 and 9 were then added and the reaction mixture was allowed to stir for 30 minutes and cooled to ambient temperature.

[0255] Table 1. Components used to prepare crosslinker I

[0256]

[0257]

[0258] 1 Rubinate M, available from Huntsman Corporation.

[0259] 21-Methoxy-2-propanol, available from Dow.

[0260] Preparation of cationic amine functionalized polyepoxide-based resin (resin system I). A cationic amine functionalized polyepoxide-based polymer resin suitable for formulating an electrodepositable coating composition was prepared in the following manner. Components 2-4 listed in Table 1 below were combined in a flask set to total reflux by stirring under nitrogen. The mixture was heated to 130°C and allowed to exotherm (maximum 170°C). A temperature of 145°C was established in the reaction mixture, and the reaction mixture was then kept for 1.5 hours. Components 5-7 were then introduced into the reaction mixture, and a temperature of 100°C was established in the reaction mixture. Components 8 and 9 were then quickly added to the reaction mixture, and the reaction mixture was allowed to exotherm. A temperature of 110°C was established in the reaction mixture, and the reaction mixture was kept for 1 hour. After the hold, the heat source was removed from the reaction mixture, and component 10 was slowly introduced. The contents in the agitated flask were cooled to room temperature. The solid content of the resulting resin synthesis product I was 86.9% by weight.

[0261] Table 2. Components used to prepare resin system I

[0262]

[0263]

[0264] 1 Epon 880, available from Hexion Corporation.

[0265] 2 See Example Cross-Linker I above.

[0266] 3 1-Methoxy-2-propanol, available from The Dow Chemical Company.

[0267] Preparation of Crosslinker II. A blocked polyisocyanate crosslinker suitable for electrodepositable coating compositions was prepared in the following manner. Components 2-4 listed in Table 3 below were mixed in a flask set to 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 maintained at 100°C for one hour. Components 6 and 7 were then added to the flask, and the mixture was mixed for 30 minutes and cooled to ambient temperature.

[0268] Table 3. Components used to prepare crosslinker II

[0269]

[0270] 1 Rubinate M, available from Huntsman Corporation.

[0271] 2 1-Methoxy-2-propanol, available from Dow.

[0272] Preparation of cationic amine functionalized polyepoxide-based resin (resin system II). A cationic amine functionalized polyepoxide-based polymer resin suitable for formulating an electrodepositable coating composition was prepared in the following manner. Components 4-4 listed in Table 1 below were combined in a flask set to total reflux by stirring under nitrogen. The mixture was heated to 130°C and allowed to release heat (maximum 170°C). A temperature of 145°C was established in the reaction mixture, and the reaction mixture was then kept for 1.5 hours. Component 5 was then introduced into the reaction mixture, and a temperature of 100°C was established in the reaction mixture, and allowed to mix for 10 minutes. Components 6 and 7 were then introduced into the reaction mixture and allowed to mix for 10 minutes. Components 8 and 9 were then quickly added to the reaction mixture, and the reaction mixture was allowed to release heat. A temperature of 110°C was established in the reaction mixture, and the reaction mixture was kept for 1 hour. After holding, the heat source was removed from the reaction mixture, and component 10 was slowly introduced. The contents of the flask were stirred for at least 15 minutes while cooling to room temperature. The resulting resin synthesis product II had a solid content of 86.2% by weight.

[0273] Table 4. Components used to prepare resin system II

[0274]

[0275] 1 Epon 880, available from Hexion Corporation.

[0276] 2 See Example Cross-linker II above.

[0277] 3 1-Methoxy-2-propanol, available from The Dow Chemical Company.

[0278] Preparation of cationic amine functionalized polyepoxide-based resin (resin system III). A cationic amine functionalized polyepoxide-based polymer resin suitable for formulating an electrodepositable coating composition was prepared in the following manner. Components 5-3 listed in Table 1 below were combined in a flask set to total reflux by stirring under nitrogen. The mixture was heated to a temperature of 130°C and mixed. Component 4 was added to the mixture, and a temperature of 135°C was established and maintained for at least 1 hour until the target epoxy equivalent of 549 was reached. Component 5 was then added to the mixture, and a temperature of 100°C was established in the reaction mixture. Components 6 and 7 were then added to the reaction mixture and allowed to exotherm. A temperature of 95°C was established in the reaction mixture, and the mixture was stirred for 3 hours. The contents of the flask were then dissolved in the pre-blended 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 solid content of 45% by weight.

[0279] Table 5. Components used to prepare resin system III

[0280] serial number Components Weight parts (g) 1 <![CDATA[Diglycidyl bisphenol A 1 > 401.9 2 Bisphenol A 122.5 3 Butyl Carbitol Formaldehyde 58.50 4 Ethyltriphenylphosphonium iodide 0.400 5 Butyl Carbitol Formaldehyde 100.1 6 <![CDATA[Jeffamine D2000 2 ]]> 1449 7 Butyl Carbitol Formaldehyde 60.40 8 lactic acid 31.00 9 Deionized water 1119 10 Deionized water 249.6

[0281] 1 Epon 880, available from Hexion Corporation.

[0282] 2 Jeffamine D2000, available from Huntsman.

[0283] Preparation of cationic amine functionalized polyepoxide-based resin (resin system IV). A cationic amine functionalized polyepoxide-based polymer resin suitable for formulating an electrodepositable coating composition was prepared in the following manner. Components 6-4 listed in Table 1 below were combined in a flask set to total reflux by stirring under nitrogen. The mixture was heated to 130°C and allowed to exotherm (maximum 170°C). A temperature of 145°C was established in the reaction mixture, and the reaction mixture was then kept for 1.5 hours. Component 5 was then introduced into the reaction mixture, and a temperature of 100°C was established in the reaction mixture, and allowed to mix for 10 minutes. Component 7 was then introduced into the reaction mixture and allowed to mix for 10 minutes. Components 7 and 8 were then quickly added to the reaction mixture, and the reaction mixture was allowed to exotherm. A temperature of 110°C was established in the reaction mixture, and the reaction mixture was kept for 1 hour. After holding, the heat source was removed from the reaction mixture, and component 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 solid content of 86.2% by weight.

[0284] Table 6. Components used to prepare resin system IV

[0285]

[0286]

[0287] 1 Epon 880, available from Hexion Corporation.

[0288] 2 1-Methoxy-2-propanol, available from The Dow Chemical Company.

[0289] Preparation of Electrodepositable Coating Compositions of Examples 1-5

[0290] Sources of Formulation Additives and Chemicals: Chemicals used to formulate the electrophoretic coating bath were obtained from various suppliers. Butyl carbitol formal was commercially available from BASF as MAZON 1651 (98% purity). Ethylene glycol monobutyl ether (butyl cellosolve) was commercially available from Millipore Sigma / 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 at 98% purity. Sulfamic acid and phosphoric acid (85% active by weight in water) were obtained from PPG Industries Inc.

[0291] Example 1: A highly pigmented, electrodepositable coating composition was prepared as follows. Components 1-3 listed in Table 7 below were combined in a stainless steel beaker and mixed at 40°C under high shear (2500 RPM, using a 1.5-inch Cowles blade driven by a Fawcett air motor model 103A) for 5 minutes. The temperature was raised to above 60°C and the mixture was maintained as mixed for one hour, after which the dispersion was measured using a Hegman meter. A minimum reading of 5 was required for adequate dispersion.

[0292] For the dispersion step, a mixture of components 4-6 was added to the clay / resin 1 paste. A temperature of less than 60°C was established, and the dispersion was mixed with a high-lift blade at 1500 RPM for one hour. After dispersion, the dispersion was allowed to cool 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 dispersed formulation and allowed to mix at ambient temperature for one hour to complete the high-solids feed. To create the electrocoat bath composition, the high-solids feed was further diluted with component 9 to 25% by weight solids.

[0293] Table 7. Components used to prepare Example 1

[0294]

[0295]

[0296] 1 ASP200 clay, available from BASF.

[0297] 2 See Example Resin System I above.

[0298] 3 See Example Resin System III above.

[0299] 4 Dibutyltin dioxide paste, available from PPG Industries.

[0300] Example 2: A highly pigmented, electrodepositable coating composition was prepared as follows. Components 1-3 listed in Table 8 below were combined in a stainless steel beaker and mixed at 40°C under high shear (2500 RPM, using a 1.5-inch Cowles blade driven by a Fawcett air motor model 103A) for 5 minutes. The temperature was raised to above 60°C and the mixture was maintained as mixed for one hour, after which the dispersion was measured using a Hegman meter. A minimum reading of 5 was required for adequate dispersion.

[0301] For the dispersion step, a mixture of components 4-6 was added to the clay / resin 1 paste. A temperature of less than 60°C was established, and the dispersion was mixed with a high-lift blade at 1500 RPM for one hour. After dispersion, the dispersion was allowed to cool 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 dispersed formulation and allowed to mix at ambient temperature for one hour to complete the high-solids feed. The high-solids feed was further diluted to 25% by weight solids with component 9. To create the electrocoat bath composition, the bath was heated to 95°F and component 10 was added. The electrocoat bath composition was allowed to mix for two hours after the addition before repeating the test.

[0302] Table 8. Components used to prepare Example 2

[0303]

[0304]

[0305] 1 ASP200 clay, available from BASF.

[0306] 2 See Example Resin System I above.

[0307] 3 See Example Resin System III above.

[0308] 4 Dibutyltin dioxide paste, available from PPG Industries.

[0309] 5 A 10% solution was prepared by stirring 10% by weight of POVAL 35-80 (available from Kuraray Co.) in deionized water at 85°C for 15 minutes and then cooling for 1 hour before use.

[0310] Comparative Examples 3-5: Examples 2 to 4 were prepared by the following general procedure. Components 1-3 listed in Table 9 below were combined in a stainless steel beaker and mixed at 40°C under high shear (2500 RPM, using a 1.5-inch Cowles blade driven by a Fawcett air motor model 103A) for 5 minutes. The temperature was raised to above 60°C and the mixture was maintained as mixed for one hour, after which the dispersion was measured using a Hegman meter. A minimum reading of 5 was required for adequate dispersion.

[0311] For the dispersion step, a mixture of components 4-6 was added to the clay / resin 1 paste. A temperature of less than 60°C was established, and the dispersion was mixed with a high-lift blade at 1500 RPM for one hour. After dispersion, the dispersion was allowed to cool to ambient temperature, and component 7 was added. Component 8 was then added to the dispersed formulation and allowed to mix at ambient temperature for one hour to complete the high-solids feed. To create the electrocoat bath composition, the high-solids feed was further diluted with component 9 to 25% solids by weight, except for Example 4, where component 9 was diluted to 15% solids.

[0312] Table 9. Components used to prepare Comparative Examples 3-5

[0313]

[0314]

[0315] 1 ASP200 clay, available from BASF.

[0316] 2 See Example Resin System I above.

[0317] 3 See Example Resin System III above.

[0318] 4 Dibutyltin dioxide paste, available from PPG Industries.

[0319] Test Methods Used to Evaluate Examples 1-5

[0320] Evaluation of Burred Edge Coverage: CRS panels pretreated with zinc phosphate (C700 / DI; Item No. 28630, available from ACT, Hillsdale, Michigan) were cut in half to produce 4" x 6" panels. 0.25 inches was then removed from one side of the panel to produce a 3.75" x 6" panel with a burred edge on each side. These burred edges were used to test the ability of the electrocoat to cover sharp edge areas. The panels were immersed in the electrocoat and electrodeposited using a DC powered rectifier (Xantrax Model XFR600-2, Elkhart, Indiana; or Sorensen XZG 300-5.6, Ameteck, Berwyn, Pennsylvania). The target film build was 1.0 mil (25.4 microns) on the vertical sides of the panels. The exact coating conditions for each coating are shown in Table 10. After the panels were e-coated, they were rinsed with deionized water and baked in an electric oven (Despatch Model LFD-1-42) at 177°F for 30 minutes.

[0321] The three panels coated with each electrophoretic paint composition were placed in an ASTM-B117 neutral salt spray corrosion test with the burr edge facing upward for a total of 7 days (168 hours). After the test, the panels were rinsed with isopropyl alcohol to remove residual water and air-dried. The amount of corrosion along the burr edge was then measured and reported in Table 11. Corrosion was quantified by manually measuring the total length of the burr edge, which did not show red rust and was protected from corrosion. The uncorroded length was divided by the total length of the burr edge to provide the percentage of the covered edge. This test method is referred to as the edge coverage test method in this article.

[0322] Evaluation of Elongation Flexibility: CRS panels pretreated with zinc phosphate (C700 / DI; Item No. 28630, available from ACT, Inc., Hillsdale, Michigan) were cut in half to produce 4" x 6" panels. The panels were immersed in the electrophoretic paint and electrodeposited using a DC powered rectifier (Xantrax Model XFR600-2, Elkhart, Indiana; or Sorensen XZG 300-5.6, AMETEK, Berwyn, Pennsylvania). The target film build was 1.0 mil (25.4 microns) on the vertical sides of the panels. The exact coating conditions for each coating are shown in Table 10. After the panels were electrophoretically coated, they were rinsed with deionized water and baked in an electric oven (Despatch Model LFD-1-42) at 177°F for 30 minutes.

[0323] Two panels coated with each electrocoat composition were subjected to elongation flexibility testing using mandrel bending according to ASTM D522. The panels were placed vertically in the instrument, locked in place, and bent over the instrument's tapered fulcrum. Adhesive tape was repeatedly applied to the bend area and pulled off to remove any weakly adhering coating until no additional coating adhered to the tape. Delamination area was measured using a ruler from the edge of the bend area to the point where the coating no longer delaminated. The amount of delamination along the tapered bend is reported in Table 11.

[0324] Evaluation of the coating glass transition temperature: To obtain the glass transition temperature, a free film of the example electrophoretic paint was first generated using a conductive electrophoretic paint. The formulation and use of the conductive electrophoretic paint are described in detail below.

[0325] Conductive electrophoretic paint was prepared using commercially available PPG products with 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 one hour. The material was then used to electrophoretically paint panels using technical bulletin specifications.

[0326] CRS panels pretreated with zinc phosphate (C700 / DI; Item No. 28630, available from ACT, Inc., Hillsdale, Michigan) were cut in half to produce 4" x 6" panels. The panels were immersed in conductive electrophoretic paint and electrodeposited using a DC powered rectifier (Xantrax Model XFR600-2, Elkhart, Indiana; or Sorensen XZG 300-5.6, Ametek, Berwyn, Pennsylvania). The target film build was 0.5 to 0.7 mils (12.7 to 17.8 microns) on the vertical sides of the panels. To achieve the target film build for each panel, the electrophoretic paint bath was maintained at 80°F and a voltage of 115 volts was used with a limit setting of 0.75 amps. Coating was continued until 40 coulombs were generated. After the panels were electrophoretically coated, they were rinsed with deionized water and baked in an electric oven (Despatch Model LFD-1-42) at 219°C for 90 minutes.

[0327] The panels coated in the conductive electrophoretic paint were then immersed in the example electrophoretic paint and electrodeposited using a DC powered rectifier (Xantrax Model XFR600-2, Elkhart, Indiana; or Sorensen XZG 300-5.6, AMETEK, Berwyn, Pennsylvania). The target film build was 1.0 mil (25.4 microns) on the vertical face of the panel. The exact coating conditions for each coating are shown in Table 10. After the panels were electrophoretically coated, they were rinsed with deionized water and baked in an electric oven (Despatch Model LFD-1-42) at 177°F for 30 minutes. The example electrophoretic paint was then peeled from the conductive electrophoretic paint panels and used to measure the glass transition temperature.

[0328] Glass transition temperature (T g ) were measured using a dynamic mechanical analyzer (DMA). A TA Instruments Discovery DMA 850 device was used in tensile mode with a preload force of 10 mN, an amplitude of 15 μm (tensile strain <0.3%), a static stress / dynamic stress amplitude ratio ("force tracking") of 125%, and an oscillation frequency of 1 Hz. The samples were first cut into a rectangular shape characterized by a width of 7 mm, a gauge length of 15 mm, and a thickness of 25 μm. After loading each film specimen under tensile stress at room temperature, they were cooled to -125°C, thermally equilibrated, and heated to 200°C at a rate of 3°C / min. T g Determined by the peak temperature value of the loss tangent (tanδ). Measured T g Listed in Table 11.

[0329] Evaluation of Cured Coating Structures: CRS panels pretreated with zinc phosphate (C700 / DI; Item No. 28630, available from ACT, Inc., Hillsdale, Michigan) were cut in half to produce 4" x 6" panels. The panels were immersed in the electrophoretic paint and electrodeposited using a DC powered rectifier (Xantrax Model XFR600-2, Elkhart, Indiana; or Sorensen XZG 300-5.6, AMETEK, Berwyn, Pennsylvania). The target film build was 1.0 mil (25.4 microns) on the vertical sides of the panels. The exact coating conditions for each coating are shown in Table 10. After the panels were electrophoretically coated, they were rinsed with deionized water and baked in an electric oven (Despatch Model LFD-1-42) at 177°F for 30 minutes.

[0330] The panels were then prepared for TEM analysis. The panels were cut to size and embedded in EMBed-812 epoxy resin and cured at 60°C for 24 hours. Thin sections (<80 nm) were then ultramicrotomed and collected on Cu TEM grids. Brightfield images were acquired on a Tecnai T20 TEM operated at 200 kV, and images for each of Examples 1-5 are included in the accompanying image. Figure 1 The maximum Feret diameter of the low-density domains was determined by measuring 10 domains in three different images using ImageJ. The measured domain sizes are listed in Table 11.

[0331] Evaluation of Examples 1-5

[0332] As shown in Tables 10 and 11, the electrodeposited coatings had a loading of platy pigments with a pigment to binder ratio of at least 0.4:1 and a plurality of T values ​​indicative of resin domain formation. g , resulting in improved edge corrosion resistance and elongational flexibility. Further, the size of these domains can be adjusted to modify these properties.

[0333] Table 10. Electrodeposition conditions for Examples 1-5

[0334] condition Example 1 Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Voltage (V) 250 250 110 150 285 Current (amperes) 0.5 0.5 0.5 0.5 0.5 Time (minutes) 2 2 2 2 2

[0335] Table 11. Evaluation of the electrodeposition coating compositions of Examples 1-5

[0336]

[0337] Preparation of Electrodepositable Coating Compositions of Examples 6-9

[0338] Comparative Examples 6 and 7: A highly pigmented, electrodepositable coating composition was prepared as follows. Components 1-4, listed in Table 12 below, were combined in a stainless steel beaker and mixed at 40°C under high shear (2500 RPM, using a 1.5-inch Cowles blade driven by a Fawcett air motor model 103A) for 5 minutes. The temperature was raised to above 60°C and the mixture was maintained as described for one hour, after which the dispersion was measured using a Hegman meter. A minimum reading of 5 was required for adequate dispersion.

[0339] For the dispersion step, a mixture of components 5 and 6 was added to the clay / resin II paste. A temperature of less than 60°C was established, and the dispersion was mixed with a high-lift blade at 1500 RPM for one hour. After dispersion, the dispersion was allowed to cool 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 dispersed formulation and allowed to mix at ambient temperature for one hour to complete the high-solids feed. To create the electrocoat bath composition, the high-solids feed was further diluted with component 10 to 25% by weight solids.

[0340] Table 12. Components used to prepare Comparative Example 6 and Example 7

[0341] serial number Components Comparative Example 6 Example 7 1 <![CDATA[ASP200 clay 1 > 435 439 2 <![CDATA[Resin II 2 > 837 707 3 phosphoric acid 6.05 5.09 4 Deionized water 83.4 70.2 5 Sulfamic acid 10.2 8.57 6 Deionized water 765.2 700.4 7 <![CDATA[Resin III 3 > 0 271.1 8 Deionized water 801 724 9 <![CDATA[E6278 4 ]]> 28.7 26.9 10 Deionized water 1780 1792

[0342] 1 ASP200 clay, available from BASF.

[0343] 2 See Example Resin System II above.

[0344] 3 See Example Resin System III above.

[0345] 4 Dibutyltin dioxide paste, available from PPG Industries.

[0346] Comparative Example 8: A highly pigmented, electrodepositable coating composition was prepared as follows. Components 1-4 listed in Table 13 below were combined in a stainless steel beaker and mixed at 40°C under high shear (2500 RPM, using a 1.5-inch Cowles blade driven by a Fawcett air motor model 103A) for 5 minutes. The temperature was raised to above 60°C, and the mixture was maintained as described for one hour, after which the dispersion was measured using a Hegman meter. A minimum reading of 5 was required for adequate dispersion.

[0347] For the dispersion step, a mixture of components 5 and 6 was added to the clay / resin II / resin IV paste. A temperature of less than 60°C was established, and the dispersion was mixed with a high-lift blade at 1500 RPM for one hour. The final solids content of this dispersed paste was 30% by weight. Component 7 was then added to the dispersed formulation and allowed to mix at ambient temperature for one hour to complete the high-solids feed. To create the electrocoat bath composition, the high-solids feed was further diluted with component 8 to 25% by weight solids.

[0348] Table 13. Components used to prepare Comparative Example 8

[0349] serial number Components Comparative Example 8 1 <![CDATA[Resin II 2 > 597 2 <![CDATA[Resin IV 3 > 494 3 phosphoric acid 8.35 4 Deionized water 115 5 Sulfamic acid 14.1 6 Deionized water 2176 7 <![CDATA[E6278 4 ]]> 40.3 8 Deionized water 689

[0350] 1 ASP200 clay, available from BASF.

[0351] 2 See Example Resin System II above.

[0352] 3 See Example Resin System IV above.

[0353] 4 Dibutyltin dioxide paste, available from PPG Industries.

[0354] Comparative Example 9: A highly pigmented, electrodepositable coating composition was prepared as follows. Components 1-3 listed in Table 14 below were combined in a stainless steel beaker and mixed at 40°C under high shear (2500 RPM, using a 1.5-inch Cowles blade driven by a Fawcett air motor model 103A) for 5 minutes. The temperature was raised to above 60°C, and the mixture was maintained as mixed for one hour, after which the dispersion was measured using a Hegman meter. A minimum reading of 5 was required for adequate dispersion.

[0355] For the dispersion step, a mixture of components 4 and 5 was added to the clay / resin II paste. A temperature of less than 60°C was established, and the dispersion was mixed with a high-lift blade at 1500 RPM for one hour. After dispersion, the dispersion was allowed to cool to ambient temperature, and component 6 was added and mixed for one hour to achieve a final solids content of 30% by weight in the dispersion paste. Component 7 was then added to the dispersed formulation and allowed to mix at ambient temperature for one hour to complete the high-solids feed. To create the electrocoat bath composition, the high-solids feed was further diluted with component 8 to 25% by weight solids.

[0356] Table 14. Components used to prepare Comparative Example 9

[0357]

[0358]

[0359] 1 ASP200 clay, available from BASF.

[0360] 2 See Example Resin System II above.

[0361] 3 See Example Resin System III above.

[0362] 4 Dibutyltin dioxide paste, available from PPG Industries.

[0363] Test Methods Used to Evaluate Examples 6-9

[0364] Evaluation of Elongation Flexibility: The same test used to evaluate elongation flexibility for Examples 1-5 was used for Examples 6-9.

[0365] Evaluation of Cured Coating Structures: The same test used to evaluate resin domain formation in the cured coating structures for Examples 1-5 was used for Examples 6-9. However, for Examples 6-9, domain formation was reported as either present or absent in the coating structure.

[0366] Evaluation of Water Vapor Transmission Rate of Coatings: To obtain water vapor transmission rate, conductive electrophoretic paint was first used to generate free films of electrophoretic paints of Examples 6 to 9. The formulation and use of the conductive electrophoretic paint are described in detail below.

[0367] Conductive electrophoretic paint was prepared using commercially available PPG products with 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 one hour. The material was then used to electrophoretically paint panels using technical bulletin specifications.

[0368] CRS panels pretreated with zinc phosphate (C700 / DI; Item No. 28630, available from ACT, Inc., Hillsdale, Michigan) were cut in half to produce 4" x 6" panels. The panels were immersed in conductive electrophoretic paint and electrodeposited using a DC powered rectifier (Xantrax Model XFR600-2, Elkhart, Indiana; or Sorensen XZG 300-5.6, Ametek, Berwyn, Pennsylvania). The target film build was 0.5 to 0.7 mils (12.7 to 17.8 microns) on the vertical sides of the panels. To achieve the target film build for each panel, the electrophoretic paint bath was maintained at 80°F and a voltage of 115 volts was used with a limit setting of 0.75 amps. Coating was continued until 40 coulombs were generated. After the panels were electrophoretically coated, they were rinsed with deionized water and baked in an electric oven (Despatch Model LFD-1-42) at 219°C for 90 minutes.

[0369] The panels coated in the conductive electrophoretic paint were then immersed in the example electrophoretic paint and electrodeposited using a DC powered rectifier (Xantrax Model XFR600-2, Elkhart, Indiana; or Sorensen XZG 300-5.6, AMETEK, Berwyn, Pennsylvania). The target film build was 1.0 mil (25.4 microns) on the vertical face of the panel. The exact coating conditions for each coating are shown in Table 15. After the panels were electrophoretically coated, they were rinsed with deionized water and baked in an electric oven (Despatch Model LFD-1-42) at 177°F for 30 minutes. The example electrophoretic paint was then peeled from the conductive electrophoretic paint panels and used to measure the glass transition temperature.

[0370] Water vapor transmission rate (WVTR) was measured using a Permatran-W 3 / 34W VTR analyzer according to ASTM F-1249. Each sample was masked between two sheets of adhesive aluminum foil. The test area was 5.00 cm 2 , wherein the samples were tested at 37.8°C and 90% room humidity. This test method is referred to herein as the water vapor transmission rate test method. The measured transmission rates for Examples 6-9 are listed in Table 16.

[0371] Evaluation of Examples 6-9

[0372] The results shown in Table 16 demonstrate the effectiveness of utilizing platy pigments in combination with domains in the coating structure to provide balanced improvements in reducing water vapor transmission rate and improving the elongational flexibility of the coating.

[0373] Table 15. Electrodeposition Conditions for Examples 6-9

[0374] condition Comparative Example 6 Example 7 Comparative Example 8 Comparative Example 9 Voltage (V) 298 200 100 50 Current (amperes) 0.5 0.5 0.5 0.5 Time (minutes) 2 2 2 2

[0375] Table 16. Evaluation of the electrodeposition coating compositions of Examples 6-9

[0376]

[0377] Those skilled in the art will appreciate that, based on the foregoing disclosure, many modifications and variations are possible without departing from the broad inventive concepts described and exemplified herein. Therefore, it should be understood that the foregoing disclosure is merely illustrative of various illustrative aspects of the present application, and that those skilled in the art can readily make many modifications and variations within the spirit and scope of the present application and the appended claims.

Claims

1. A coated conductive substrate comprising an electrodeposited coating deposited from an electrodepositable coating composition, wherein the electrodeposited coating comprises: platy pigments present in a pigment to binder ratio of at least 0.4:1; and An electrodeposition adhesive, comprising: a first resin domain 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 greater than the second glass transition temperature, such as at least 20°C, such as at least 30°C, such as at least 40°C, such as at least 50°C, such as at least 60°C, such as at least 70°C, such as at least 80°C, such as at least 90°C, such as at least 100°C, such as at least 110°C, such as at least 120°C, such as at least 130°C, such as at least 140°C, such as at least 150°C, such as at least 160°C, such as at least 170°C, and the second glass transition temperature is greater than -50°C.

2. A coated conductive substrate comprising an electrodeposited coating deposited from an electrodepositable coating composition, wherein the electrodeposited coating comprises: platy pigments present in a pigment to binder ratio of at least 0.4:1; and An electrodeposition adhesive, 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.

3. An electrodeposited coating deposited from an electrodepositable coating composition, the electrodepositable coating composition comprising: platy pigments present in a pigment to binder ratio of at least 0.4:1; and An electrodepositable adhesive comprising: a first resin domain 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 greater than the second glass transition temperature, such as at least 20°C, such as at least 30°C, such as at least 40°C, such as at least 50°C, such as at least 60°C, such as at least 70°C, such as at least 80°C, such as at least 90°C, such as at least 100°C, such as at least 110°C, such as at least 120°C, such as at least 130°C, such as at least 140°C, such as at least 150°C, such as at least 160°C, such as at least 170°C, and the second glass transition temperature is greater than -50°C.

4. An electrodeposited coating deposited from an electrodepositable coating composition, the electrodepositable coating composition comprising: platy pigments present in a pigment to binder ratio of at least 0.4:1; and An electrodepositable adhesive 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.

5. The coated conductive substrate or electrodeposited coating according to any one of the preceding claims, wherein the plate-like pigments have an average equivalent spherical diameter of at least 50 nm.

6. The coated conductive substrate or electrodeposited coating of any one of the preceding claims, wherein the platy pigment comprises a phyllosilicate pigment, wherein optionally, the phyllosilicate pigment comprises mica, chlorite, serpentine, talc, a clay mineral, or a combination thereof, wherein optionally, the clay mineral comprises kaolin, montmorillonite clay, or a combination thereof.

7. A coated conductive substrate or electrodeposited coating according to any one of the preceding claims, wherein the plate-shaped pigment is present in a pigment to binder ratio of 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.

8. The coated conductive substrate or electrodeposited coating according to any one of the preceding claims, wherein the electrodeposition binder comprises an organic binder comprising a residue 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. The coated conductive substrate or electrodeposited 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 coated conductive substrate or electrodeposition coating according to claim 8 or 9, wherein the organic resin component comprises: (1) an addition polymer comprising the polymerization product of a polymeric dispersant and a second-stage ethylenically unsaturated monomer composition comprising a second-stage hydroxy-functional (meth)acrylamide monomer and / or a second-stage hydroxy-functional (meth)acrylate monomer; and (2) a hydroxy-functional addition polymer comprising structural units, at least 70% of which comprise Formula VIII: —[—C(R 1 )2—C(R 1 )(OH)—]—(VIII), Each R 1 is independently one of hydrogen, an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an alkylcycloalkyl group, a substituted alkylcycloalkyl group, a cycloalkylalkyl group, a substituted cycloalkylalkyl group, an aryl group, a substituted aryl group, an alkylaryl group, a substituted alkylaryl group, a cycloalkylaryl group, a substituted cycloalkylaryl group, an arylalkyl group, a substituted arylalkyl group, an arylcycloalkyl group, or a substituted arylcycloalkyl group, and the % is based on the total structural units of the hydroxy-functional addition polymer; (3) a cellulose derivative; (4) polyvinylformamide; (5) a cationic epoxy microgel; (6) a polyamine-dialdehyde adduct; (7) a polyetheramine adduct; or any combination thereof.

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

12. The coated conductive substrate or electrodeposition coating according to any one of preceding 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. A coated conductive substrate or electrodeposited coating according to any one of the preceding claims 8 to 12, wherein the organic resin component comprises a hydroxyl functional addition polymer.

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

15. The coated conductive substrate or electrodeposited coating according to any one of the preceding 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 electrodeposited coating.

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

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

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

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

20. The coated conductive substrate or electrodeposited coating according to any one of the preceding claims, wherein the second resin domain has 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.

21. A coated conductive substrate or electrodeposited coating according to any one of the preceding claims, wherein the electrodeposited coating has delamination of less than 15 mm when measured according to the mandrel bend test of ASTM D522; and / or wherein the electrodeposited coating has an edge coverage greater than 20% as measured by the Edge Coverage Test Method; and / or The electrodeposition coating has a thickness of less than 55 g / m 2 Water Vapor Transmission Rate (WVTR) per day as measured by the Water Vapor Transmission Rate (WVTR) test method.

22. The coated conductive substrate or electrodeposited coating according to any one of the preceding claims, wherein the electrodeposited coating further comprises a third glass transition temperature that is less than the second glass transition temperature.

23. The coated conductive substrate or electrodeposited 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. The coated conductive substrate or electrodeposited coating according to any one of the preceding claims, wherein the coated conductive substrate does not include a pretreatment layer between the substrate and the electrodeposited coating, and / or wherein the coated conductive substrate does not include any intervening coating between the substrate and the electrodeposited coating.

25. The coated conductive substrate or electrodeposited coating according to any one of the preceding claims, wherein the electrodeposited coating further comprises a flame retardant pigment, a hybrid organic-inorganic material and / or an organic flame retardant additive.

26. 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 platy pigment present in a pigment to binder ratio of at least 0.4:

1.

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

28. An electrodepositable coating composition according to claim 26 or 27, wherein the platy pigment comprises a phyllosilicate pigment.

29. The electrodepositable coating composition of claim 28, wherein the layered silicate pigment comprises mica, chlorite, serpentine, talc, a clay mineral, or a combination thereof.

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

31. The electrodepositable coating composition of any one of claims 26 to 30, wherein the plate-like pigment is present in a pigment to binder ratio of 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.

32. The electrodepositable coating composition of any one 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 electrodepositable coating composition of any one of claims 26 to 32, wherein the organic resin component comprises: (1) an addition polymer comprising the polymerization product of a polymeric dispersant and a second-stage ethylenically unsaturated monomer composition comprising a second-stage hydroxy-functional (meth)acrylamide monomer and / or a second-stage hydroxy-functional (meth)acrylate monomer; and (2) a hydroxy-functional addition polymer comprising structural units, at least 70% of which comprise Formula VIII: —[—C(R 1 )2—C(R 1 )(OH)—]—(VIII), Each R 1 is independently one of hydrogen, an alkyl group, a substituted alkyl group, a cycloalkyl group, a substituted cycloalkyl group, an alkylcycloalkyl group, a substituted alkylcycloalkyl group, a cycloalkylalkyl group, a substituted cycloalkylalkyl group, an aryl group, a substituted aryl group, an alkylaryl group, a substituted alkylaryl group, a cycloalkylaryl group, a substituted cycloalkylaryl group, an arylalkyl group, a substituted arylalkyl group, an arylcycloalkyl group, or a substituted arylcycloalkyl group, and the % is based on the total structural units of the hydroxy-functional addition polymer; (3) a cellulose derivative; (4) polyvinylformamide; (5) a cationic epoxy microgel; (6) a polyamine-dialdehyde adduct; (7) a polyetheramine adduct; or any combination thereof.

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

35. The electrodepositable coating composition of any one 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. An electrodepositable coating composition according to any one of the preceding claims 26 to 35, wherein the organic resin component comprises a hydroxyl functional addition polymer.

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

38. The electrodepositable coating composition of any one of claims 33 to 37, 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 resin solids of the electrodepositable coating composition.

39. An electrodepositable coating composition according to any one of the preceding claims 26 to 37, wherein the organic resin component comprises a polyetheramine adduct.

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

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

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

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