Compositions, systems and methods for treating substrates

Abstract

The present disclosure relates to a detergent-coating agent composition comprising: a Group IVB metal in an amount of from 50 ppm to 8,000 ppm based on the total weight of the detergent-coating agent composition, and a Group IVB metal in an amount of from 50 ppm to 8,000 ppm based on the total weight of the detergent-coating agent composition; an electropositive metal; a builder comprising a phosphonate and / or a sugar alcohol; and a detergent-coating agent surfactant in an amount of from 50 ppm to 20,000 ppm based on the total weight of the detergent-coating agent composition. The present disclosure also relates to systems and methods for treating a substrate comprising any of the detergent-coating agent compositions disclosed herein and an electrodepositable coating composition. The present disclosure also relates to substrates treated by any of the detergent-coating agent compositions, systems and / or methods disclosed herein.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to compositions, systems, and methods for treating substrates. BACKGROUND

[0002] It is common to use protective coatings on metal substrates to improve corrosion resistance and paint adhesion. Typically, the substrate surface is treated by sequentially applying (1) a cleaner composition, (2) a cleaner-coat composition, and (3) an electrodepositable coating composition. SUMMARY

[0003] Disclosed herein is a cleaner-coat composition comprising: a Group IVB metal in an amount of 50 ppm to 8,000 ppm based on the total weight of the cleaner-coat composition; a positively electronegative metal; a builder comprising a phosphonate and / or a sugar alcohol; and a cleaner-coat surfactant in an amount of 50 ppm to 20,000 ppm based on the total weight of the cleaner-coat composition.

[0004] The present disclosure further relates to a system for treating a substrate, the system comprising (a) any of the cleaner-coat compositions disclosed herein for treating at least a portion of a surface of a substrate; and (b) any of the electrodepositable coating compositions disclosed herein for at least partially coating the portion of the surface of the substrate treated with the cleaner-coat composition.

[0005] The present disclosure further relates to a system for treating a substrate, the system comprising a cleaner-coat composition comprising: a Group IVB metal in an amount of 50 ppm to 8,000 ppm based on the total weight of the cleaner-coat composition; a positively electronegative metal, such as copper; and a surfactant in an amount of 50 ppm to 20,000 ppm based on the total weight of the cleaner-coat composition for treating at least a portion of a surface of a substrate; and an electrodepositable coating composition for at least partially coating the portion of the surface of the substrate treated with the cleaner-coat composition.

[0006] The present disclosure further relates to a method for coating a substrate, the method comprising applying any of the cleaner-coat compositions disclosed herein to at least a portion of a surface of a substrate.

[0007] This disclosure further relates to a method of treating a substrate, the method comprising: applying any of the cleaning agent-coating compositions disclosed herein to at least a portion of the surface of the substrate; and applying any of the electrodeposable coating compositions disclosed herein to at least a portion of the surface of the substrate to which the cleaning agent-coating composition has been applied.

[0008] This disclosure further relates to a substrate that can be processed by any of the systems disclosed herein.

[0009] This disclosure further relates to a substrate that is treated with any of the methods disclosed herein. Detailed Implementation

[0010] For the purposes of the following detailed description, it should be understood that this disclosure may take various alternative variations and sequences of steps unless the contrary is explicitly stated. Furthermore, except in any operational instance or where otherwise indicated, all figures such as those representing values, quantities, percentages, ranges, subranges, and fractions may be interpreted as if they begin with the word “about,” even if the term is not explicitly stated. Therefore, unless otherwise stated, the numerical parameters set forth in the following description and the appended claims are approximations that may vary according to the desired characteristics to be obtained through this disclosure. At least, and not in an attempt to limit the application of the equivalence principle to the scope of the claims, each numerical parameter should be interpreted at least according to the number of significant figures reported and by applying common rounding techniques. In the case of closed or open numerical ranges described herein, all figures, values, quantities, percentages, subranges, and fractions within or covered by such numerical ranges shall be considered as specifically included in and belonging to the original disclosure of this application as if such figures, values, quantities, percentages, subranges, and fractions had been fully and explicitly stated.

[0011] Although the numerical ranges and parameters described in this disclosure are approximate, the numerical values ​​illustrated in the specific examples are reported as precisely as possible. However, any numerical value inherently contains some error that is necessarily caused by the standard deviation found in its corresponding test measurement results.

[0012] As used herein, unless otherwise stated, plural terms may cover their singular counterparts, and vice versa. For example, although this document refers to “a” group IVB metal and “a” positively charged metal, combinations of these components (i.e., multiples of these components) may be used.

[0013] In addition, in this application, unless otherwise expressly stated, the use of “or” means “and / or”, even if “and / or” can be explicitly used in certain situations.

[0014] As used herein, "comprising," "containing," and like terms are to be understood from the context to mean including whatever follows the term from the standpoint of open- ended language that does not foreclose additional, unrecited elements, material, ingredients, or method steps. As used herein, "consisting of" is to be understood from the context as excluding any element, ingredient, or method step not specified. As used herein, "consisting essentially of" is to be understood from the context as including elements, ingredients, or method steps that do not materially affect the basic and novel characteristics of the described composition, structure, or method. Open-ended terminology includes closed-ended terminology, e.g., "comprising" includes "consisting of" and "consisting essentially of."

[0015] As used herein, the terms "on," "onto," "applied on," "applied onto," "formed on," "deposited on," "deposited onto" mean formed, covered, deposited, or provided on a surface but not necessarily in contact with the surface. For example, a composition "applied to" a substrate does not exclude the presence of one or more other intermediate coatings of the same or different compositions between the composition and the substrate.

[0016] As used herein, "system" refers to a set or suite of compositions used to treat a substrate to form a treatment stack on the treated substrate. The compositions are recited in a particular order for convenience only and are not intended to limit the order in which the compositions are used to treat the substrate.

[0017] As used herein, "treatment stack" refers to a plurality of coatings formed on a surface of a substrate.

[0018] As used herein, "cleaner-coat er composition" refers to a composition that is formulated to clean and / or de -g rease a surface of a substrate to remove grease, dirt, oil, and / or other foreign matter while also serving as a pretreatment composition.

[0019] As used herein, "pretreatment composition" refers to a composition that is capable of reacting with and chemically altering and bonding to a surface of a substrate to form a film that provides corrosion protection. The pretreatment composition can be an aqueous composition.

[0020] As used herein, "Group IVB metal" refers to the elements in Group IVB of the CAS version of the Periodic Table of the Elements as shown in, for example, Handbook of Chemistry and Physics, 63rd edition (1983), which corresponds to Group 4 in the actual IUPAC numbering.

[0021] As used herein, “Group IVB metal compound” refers to a compound comprising at least one element in Group IVB of the CAS version of the Periodic Table of the Elements.

[0022] As used herein, “surfactant” refers to a molecule capable of suspending, encapsulating, or emulsifying organic-containing contaminants. Surfactants comprise a hydrophilic portion and a hydrophobic portion, which reduce the surface tension between two liquids, a liquid and a gas, or a liquid and a solid.

[0023] As used herein, “sequestering agent” refers to a compound capable of removing metals from a composition by, for example, chelation, ionic interaction, or precipitation. Sequestering agents do not have emulsifying properties.

[0024] As used herein, “coating composition” refers to a composition, such as a solution, mixture, or dispersion, capable of producing a coating on a portion of a substrate. As used herein, “coating” includes films, layers, and the like.

[0025] As used herein, “curing agent” refers to any reactive material that can be added to cure a composition. As used herein, the term “cure,” “cured,” or like terms mean to react the reactive functionalities of the components forming the composition to form a coating or bond.

[0026] As used herein, “salt” refers to an ionic compound composed of metal or nonmetal cations and nonmetal anions and having a total charge of zero. Salts can be hydrated or anhydrous.

[0027] As used herein, “aqueous composition” or “aqueous coating composition” refers to a solution or dispersion in a medium comprising primarily water. For example, an aqueous composition can comprise water in an amount of more than 50 wt.%, or more than 70 wt.%, or more than 80 wt.%, or more than 90 wt.%, or more than 95 wt.%, based on the total weight of the composition. That is, an aqueous composition may, for example, consist essentially of water.

[0028] As used herein, the term “dispersion” refers to a two-phase transparent, translucent, or opaque system in which insoluble particles are in the dispersed phase and an aqueous medium comprising water is in the continuous phase.

[0029] As used herein, “insoluble” means not soluble in an aqueous medium.

[0030] As used herein, “soluble” means soluble in an aqueous medium.

[0031] Ambient conditions generally refer to room temperature (23 °C) and humidity conditions or temperatures and humidity conditions typically found in the area where the composition is applied to the substrate, for example, at 10 °C to 32 °C and 4% to 80% relative humidity, while slightly warm conditions are temperatures slightly above ambient temperature. As used herein, "slightly warm conditions" are temperatures ranging from greater than 32 °C to 40 °C.

[0032] As used herein, unless otherwise specified, "substantially free" means that a particular material is present in the mixture or composition (or coating formed therefrom) in an amount less than five parts per million (ppm) based on the total weight of the mixture or composition (or coating formed therefrom). As used herein, unless otherwise specified, the term "essentially free" means that a particular material is present in the mixture or composition (or coating formed therefrom) in an amount of 1 ppm based on the total weight of the mixture or composition (or coating formed therefrom). As used herein, unless otherwise specified, the term "completely free" means that a particular material is present in the mixture or composition (or coating formed therefrom) in an amount less than one part per billion (ppb) based on the total weight of the mixture or composition (or coating formed therefrom) or such material is below the detection limit of common analytical techniques. When a mixture or composition (or coating formed therefrom) is substantially free, essentially free, or completely free of a particular material, this means that such material is excluded from the mixture or composition (or coating formed therefrom) in any form, unless such material can be inadvertently present due to, for example, carryover from a previous processing bath in a processing line, contamination from the substrate, and the like.

[0033] As used herein, unless otherwise disclosed herein, the term "total composition weight," "total weight of the composition," or like terms refer to the total weight of all ingredients present in the respective composition, including any carriers and solvents.

[0034] As noted above, the present disclosure is directed to a cleaner-coater composition comprising: a Group IVB metal in an amount of 50 ppm to 8,000 ppm based on the total weight of the cleaner-coater composition; a positively electronegative metal; a builder comprising a phosphonate and / or a sugar alcohol; and a cleaner-coater surfactant in an amount of 50 ppm to 20,000 ppm based on the total weight of the cleaner-coater composition.

[0035] As noted above, the present disclosure is directed to a cleaner-coater composition comprising: a Group IVB metal in an amount of 50 ppm to 8,000 ppm based on the total weight of the cleaner-coater composition; a positively electronegative metal; a builder comprising a phosphonate and / or a sugar alcohol; and a surfactant in an amount of 50 ppm to 20,000 ppm based on the total weight of the cleaner-coater composition.

[0036] The present disclosure also relates to a system for treating a substrate, the system comprising: any of the cleaner-applicator compositions disclosed herein for treating at least a portion of a surface of a substrate; and any of the electrodepositable coating compositions disclosed herein for at least partially coating the portion of the surface of the substrate treated with the cleaner-applicator composition.

[0037] The present disclosure also relates to a system for treating a substrate, the system comprising: a cleaner-applicator composition comprising: a Group IVB metal in an amount of 50 ppm to 8,000 ppm based on the total weight of the cleaner-applicator composition; a positively electronegative metal, such as copper; and a surfactant in an amount of 50 ppm to 20,000 ppm based on the total weight of the cleaner-applicator composition, for treating at least a portion of a surface of a substrate; and an electrodepositable coating composition comprising an electrodepositable binder comprising an active hydrogen-containing, ionic salt group-containing film-forming polymer; a curing agent; and a platy pigment present at a pigment to binder ratio of at least 0.4: 1.

[0038] The present disclosure also relates to a method for coating a substrate, the method comprising applying any of the cleaner-applicator compositions disclosed herein.

[0039] The present disclosure also relates to a method of treating a substrate, the method comprising applying any of the cleaner-applicator compositions disclosed herein to at least a portion of a surface of a substrate; and applying any of the electrodepositable coating compositions disclosed herein to at least a portion of the surface of the substrate to which the cleaner-applicator composition was applied.

[0040] The present disclosure also relates to a substrate treated by any of the systems disclosed herein.

[0041] The present disclosure also relates to a substrate treated by any of the methods disclosed herein.

[0042] Cleaner-coat compositions

[0043] The cleaner-applicator composition can comprise, consist essentially of, or consist of a Group IVB metal, a positively electronegative metal, a surfactant, and optionally a builder and / or water.

[0044] The cleaner-coating agent composition can include a Group IVB metal. The Group IVB metal can include zirconium, titanium, hafnium, or combinations thereof. The Group IVB metal can be provided in the form of an acid or a salt. For example, the Group IVB metal can be a compound of zirconium, titanium, hafnium, or mixtures thereof. Suitable compounds of zirconium include, but are not limited to, hexafluorozirconic acid, alkali and ammonium salts thereof, zirconium tetrafluoride, ammonium zirconium carbonate, zirconium carboxylates, and zirconium hydroxycarboxylates, such as zirconium acetate, zirconium oxalate, ammonium zirconium glycolate, ammonium zirconium lactate, ammonium zirconium citrate, zirconium subcarbonate, zirconyl nitrate, zirconyl sulfate, oxides or hydroxides of zirconium, and mixtures thereof. Suitable compounds of titanium include, but are not limited to, hexafluorotitanic acid, fluorotitanic acid, and salts thereof. Suitable compounds of hafnium include, but are not limited to, hafnium nitrate.

[0045] The Group IVB metal can be present in the cleaner-coating agent composition in an amount of at least 50 ppm, such as at least 100 ppm, such as at least 150 ppm, such as at least 200 ppm, such as at least 500 ppm, such as at least 600 ppm, such as at least 700 ppm, such as at least 800 ppm, such as at least 900 ppm, based on the total weight of the cleaner-coating agent composition. The Group IVB metal can be present in the cleaner-coating agent composition in an amount of not more than 8,000 ppm, such as not more than 6,000 ppm, such as not more than 5,000 ppm, such as not more than 4,000 ppm, such as not more than 3,000 ppm, such as not more than 2,000 ppm, such as not more than 1,500 ppm, based on the total weight of the cleaner-coating agent composition. The Group IVB metal can be present in the cleaner-coating agent composition in an amount of 50 ppm to 8,000 ppm, such as 100 ppm to 6,000 ppm, such as 150 ppm to 4,000 ppm, such as 200 ppm to 2,000 ppm, such as 500 ppm to 5,000 ppm, such as 500 ppm to 1,500 ppm, such as 600 ppm to 4,000 ppm, such as 700 ppm to 3,000 ppm, such as 800 ppm to 2,000 ppm, such as 900 ppm to 1,500 ppm, based on the total weight of the cleaner-coating agent composition.

[0046] The cleaner-coating composition can also include a positively electronegative metal. As used herein, "positively electronegative metal" means a metal that is more positively electronegative than the metal substrate. This means that, for the purposes of the present disclosure, the term "positively electronegative metal" encompasses metals that are less susceptible to oxidation than the metal of the metal substrate being treated. As will be appreciated by those skilled in the art, the tendency of a metal to oxidize is referred to as the oxidation potential, expressed in volts, and is measured relative to a standard hydrogen electrode, which is arbitrarily assigned a zero oxidation potential. The oxidation potentials of several elements are listed in Table 1 below. If one element has a voltage value E* in the table below that is greater than the element with which it is being compared, then the element is less susceptible to oxidation than the other element.

[0047] Table 1

[0048] Element Half-cell reaction Voltage, E* Potassium K + +e→K]]> -2.93 Calcium Ca 2+ +2e→Ca -2.87 Sodium Na + +e→Na]]> -2.71 Magnesium Mg 2+ +2e→Mg -2.37 Aluminum Al 3+ +3e→Al -1.66 Zinc Zn 2+ + 2e → Zn -0.76 Iron Fe 2+ + 2e → Fe -0.44 Nickel Ni 2+ + 2e→ Ni -0.25 Tin Sn 2+ + 2e → Sn -0.14 Lead Pb 2+ +2e→Pb -0.13

[0049] Metal substrates that can be used in the present disclosure include, but are not limited to, cold rolled steel; hot rolled steel; steel coated with zinc metal, zinc compounds, or zinc alloys; hot-dipped galvanized steel; galvanized steel; steel plated with zinc alloys; aluminum alloys, aluminum plated steel; aluminum alloy plated steel; magnesium and magnesium alloys. Suitable positively electronegative metals for deposition thereon include, for example, nickel, copper, silver, and gold, and mixtures thereof.

[0050] When the positively electronegative metal comprises copper, both soluble and insoluble compounds can be used as the source of copper in the cleaner-coating composition. For example, the source of copper in the cleaner-coating composition can be a water-soluble copper compound. Specific examples of such compounds include, but are not limited to, copper sulfate, copper nitrate, cuprous thiocyanate, disodium copper ethylenediaminetetraacetate tetrahydrate, copper bromide, copper oxide, copper hydroxide, copper chloride, copper fluoride, copper gluconate, copper citrate, copper lauroylsarcosinate, copper lactate, copper oxalate, copper tartrate, copper malate, copper succinate, copper malonate, copper maleate, copper benzoate, copper salicylate, copper amino acid complexes, copper fumarate, copper glycerophosphate, copper sodium chlorophyllin, copper fluosilicate, copper fluoborate, and copper iodate, as well as copper salts of carboxylic acids such as in the homologous series of formic to capric acid, and copper salts of polyprotic acids in the oxalic to suberic acid series.

[0051] When copper supplied from such water-soluble copper compounds precipitates as an impurity in the form of copper sulfate, copper oxide, and the like, it can be desirable to add a complexing agent that inhibits the precipitation of copper, thereby stabilizing the copper as a copper complex in the composition.

[0052] The copper compound can be added as a copper complex salt such as K3Cu(CN)4 or Cu-EDTA, which can itself be stably present in the cleaner-applicator composition, i.e., not precipitate, but also can be formed by combining a complexing agent with a compound that is difficult to dissolve by itself to form a copper complex that can be stably present in the cleaner-applicator composition. Examples of this include copper cyanide complexes formed from a combination of CuCN and KCN, or CuSCN and KSCN or KCN, and Cu-EDTA complexes formed from a combination of CuSO4 and EDTA 2Na.

[0053] The electropositive metal can be present in the cleaner-applicator composition in an amount of at least 2 ppm, such as at least 10 ppm, such as at least 20 ppm, based on the total weight of the cleaner-applicator composition. The electropositive metal can be present in the cleaner-applicator composition in an amount of no more than 200 ppm, such as no more than 100 ppm, such as no more than 75 ppm, such as no more than 40 ppm, based on the total weight of the cleaner-applicator composition. The electropositive metal can be present in the cleaner-applicator composition in an amount of 2 ppm to 200 ppm, such as 2 ppm to 75 ppm, such as 10 ppm to 100 ppm, such as 20 ppm to 75 ppm, such as 20 ppm to 40 ppm, based on the total weight of the cleaner-applicator composition.

[0054] The cleaner-coat applicator composition can include a surfactant. The surfactant can include a cationic surfactant, an anionic surfactant, a non-ionic surfactant, an amphoteric surfactant, or a combination thereof. Suitable cationic surfactants include, but are not limited to, quaternary ammonium compounds (such as Tomamine Q-14-2 available from Evonik and Chemquat 508 / 40 available from PCC Group) and ethoxylated amines (such as Tomamine E-14-2 available from Evonik). Suitable anionic surfactants include, but are not limited to, alkyl diphenyl sulfonate salts (such as Dowfax 2A1 available from Dow Chemical Company), sulfates (such as Niaproof 08 available from Niacet), phosphates (such as Triton H-66 available from Dow Chemical Company), and ethers (such as Triton DF20 available from Dow Chemical Company). Suitable non-ionic surfactants include, but are not limited to, alcohol ethoxylates (such as Tomadol-1-n or Tomadol 91-6 available from Evonik Industries, SEACO 9AE available from Sea-Land Chemical Company, and Makon NF-12 available from Surfachem) and alkyl phenol ethoxylates (such as Triton X100 available from Dow Chemical Company). Suitable amphoteric surfactants include, but are not limited to, alkyl sulfobetaines (such as Mirataine ASC and Mirataine CBS available from Solvay).

[0055] The surfactant can be present in the cleaner-coat applicator composition in an amount of at least 50 ppm, such as at least 100 ppm, such as at least 200 ppm, such as at least 500 ppm, based on the total weight of the cleaner-coat applicator composition. The surfactant can be present in the cleaner-coat applicator composition in an amount of no more than 20,000 ppm, such as no more than 10,000 ppm, such as no more than 7,500 ppm, such as no more than 5,000 ppm, based on the total weight of the cleaner-coat applicator composition. The surfactant can be present in the cleaner-coat applicator composition in an amount of 50 ppm to 20,000 ppm, such as 100 ppm to 10,000 ppm, such as 200 ppm to 7,500 ppm, such as 500 ppm to 5,000 ppm, based on the total weight of the cleaner-coat applicator composition.

[0056] The cleaner-coating composition can comprise a builder. The builder can comprise, consist essentially of, or consist of a phosphonate, a phosphate (such as sodium tripolyphosphate), a carbonate, a silicate, a polycarboxylate, a polyacrylate, a gluconate, a sugar alcohol, an aminocarboxylate, or combinations thereof. Suitable phosphonates can include a monophosphonate, a diphosphonate, a polyphosphonate, or combinations thereof.

[0057] The phosphonate can include a phosphonic acid. The phosphonic acid can include a monophosphonic acid, a diphosphonic acid, a polyphosphonic acid, or combinations thereof. In examples, the diphosphonic acid can include etidronic acid or a derivative thereof. Other suitable phosphonic acids can include ethylenediaminetetra(methylene phosphonic acid) (EDTMP), diethylenetriaminepenta(methylene phosphonic acid) (DTPMPA), iminobis(methyl phosphonic acid), N-(phosphonomethyl)iminodiacetic acid hydrate, (aminomethyl)phosphonic acid, glyphosate, methylenediphosphonic acid, N,N-bis(phosphonomethyl)glycine, glyphosine, 2-phosphono 1,2,4-butanetricarboxylic acid (PBTC), amino tri(methylene phosphonic acid) (ATMP amino tri), polyvinyl phosphonic acid (PVPA), or combinations thereof.

[0058] The phosphonate can have a molecular weight (Mw) of at least 90 g / mol, such as at least 100 g / mol, such as at least 150 g / mol, such as at least 200 g / mol. The phosphonate can have a Mw of not more than 50,000 g / mol, such as not more than 40,000 g / mol, such as not more than 30,000 g / mol, such as not more than 1,000 g / mol, such as not more than 600 g / mol. The phosphonate can have a Mw in the range of 90 g / mol to 50,000 g / mol, such as 100 g / mol to 40,000 g / mol, such as 150 g / mol to 30,00 g / mol, such as 150 g / mol to 600 g / mol, such as 200 g / mol to 1,000 g / mol, such as 200 g / mol to 600 g / mol. As used herein, “Mw” refers to weight average molecular weight and means the theoretical value as determined by gel permeation chromatography using a Waters 410 differential refractometer (RI detector) with a Waters 2695 separation module using polystyrene standards, using tetrahydrofuran (THF) at a flow rate of 1 ml min -1

[0059] ​The builder can be present in the cleaner-coating agent composition in an amount of at least 10 ppm, such as at least 30 ppm, such as at least 50 ppm, based on the total weight of the cleaner-coating agent composition. The builder can be present in the cleaner-coating agent composition in an amount of not more than 2,500 ppm, such as not more than 2,000 ppm, such as not more than 1,500 ppm, based on the total weight of the cleaner-coating agent composition. The builder can be present in the cleaner-coating agent composition in an amount of 10 ppm to 2,500 ppm, such as 30 ppm to 2,000 ppm, such as 50 ppm to 1,500 ppm, based on the total weight of the cleaner-coating agent composition.

[0060] The cleaner-coating agent composition can optionally include fluoride. Fluoride can be measured as total fluoride, which includes both free fluoride and bound fluoride. As used herein, “free fluoride” means fluoride in the cleaner-coating agent composition that is not bound to a metal ion or a hydrogen ion. As used herein, “bound fluoride” means fluoride anions in solution that are ionically or covalently bound to a metal cation or a hydrogen ion. Fluoride ions so complexed cannot be measured with a fluoride ion selective electrode (ISE) unless the solution in which they reside is mixed with an ionic strength adjusting buffer (e.g., citrate anion or EDTA), which releases the fluoride ions from such complexes, at which point the fluoride ions can be measured by a fluoride ISE, and the measurement is referred to as “total fluoride.” Alternatively, total fluoride can be calculated by comparing the weight of fluoride supplied in the cleaner-coating agent composition to the total weight of the cleaner-coating agent composition.

[0061] In examples, free fluoride can be measured using, for example, an Orion DualStar dual channel benchtop meter equipped with a fluoride ion selective electrode (“ISE”), available from Thermoscientific, a fluoride ion selective electrode (“ISE”) provided by VWR International, or a fluoride ion selective electrode (“ISE”) provided by Metrohm. Fluoride ion selective combination electrodes or similar electrodes are measured as an operating parameter in the cleaner-coat composition bath. See, for example, Light and Cappuccino, Determination of fluoride in toothpaste using anion-selective electrode, J. Chem. Educ., 52:4, 247-50, April 1975. Fluoride ISEs can be standardized by immersing the electrode into a solution of known fluoride concentration and recording the reading in millivolts and then plotting these millivolt readings in a log graph. The millivolt reading of an unknown sample can then be compared to this calibration plot and the concentration of fluoride determined. Alternatively, fluoride ISEs can be used with a meter that will perform the calibration calculations internally, and thus after calibration, the concentration of an unknown sample can be read directly.

[0062] Free fluoride in the cleaner-coat composition can originate from the Group IVB metal source present in the cleaner-coat composition comprising, for example, hexafluorozirconic acid or hexafluorotitanic acid. Additionally, other complex fluorides such as H2SiF6, KHF2, or HBF4 can also be added to the cleaner-coat composition to provide free fluoride. The skilled artisan will appreciate that the presence of free fluoride in the cleaner-coat bath can impact zirconium deposition and etching of the substrate, and thus it is critical to measure this bath parameter. The level of free fluoride will depend on the pH of the cleaner-coat bath and the addition of chelating agents in the cleaner-coat bath and is indicative of the degree of association of fluoride with metal ions / protons present in the cleaner-coat bath.

[0063] Total fluoride of the cleaner-coat composition can be present in an amount of at least 60 ppm, such as at least 125 ppm, such as at least 200 ppm, such as at least 250 ppm, based on the total weight of the cleaner-coat composition. Total fluoride of the cleaner-coat composition can be present in an amount of no more than 10,000 ppm, such as no more than 7,500 ppm, such as no more than 5,000 ppm, such as no more than 3,000 ppm, such as no more than 2,500 ppm, based on the total weight of the cleaner-coat composition. Total fluoride of the cleaner-coat composition can be present in an amount of 60 ppm to 10,000 ppm, such as 125 ppm to 7,500 ppm, such as 200 ppm to 5,000 ppm, such as 250 ppm to 3,000 ppm, such as 250 ppm to 2,500 ppm, based on the total weight of the cleaner-coat composition.

[0064] The free fluoride of the cleaner-coat applicator composition can be present in an amount of at least 25 ppm, such as at least 35 ppm, such as at least 50 ppm, based on the total weight of the cleaner-coat applicator composition. The free fluoride of the cleaner-coat applicator composition can be present in an amount of not more than 750 ppm, such as not more than 600 ppm, such as not more than 500 ppm, based on the total weight of the cleaner-coat applicator composition. The free fluoride of the cleaner-coat applicator composition can be present in an amount of 25 ppm to 750 ppm, such as 35 ppm to 600 ppm, such as 50 ppm to 500 ppm, based on the total weight of the cleaner-coat applicator composition.

[0065] The cleaner-coat applicator composition can optionally further comprise lithium. The lithium metal source in the cleaner-coat applicator composition can be in the form of a salt. Non-limiting examples of suitable lithium salts include lithium nitrate, lithium sulfate, lithium fluoride, lithium chloride, lithium hydroxide, lithium carbonate, lithium iodide, and combinations thereof.

[0066] Lithium can be present in the cleaner-coat applicator composition in an amount of at least 2 ppm, such as at least 5 ppm, such as at least 25 ppm, such as at least 75 ppm, based on the total weight of the cleaner-coat applicator composition. Lithium can be present in the cleaner-coat applicator composition in an amount of not more than 1,000 ppm, such as not more than 500 ppm, such as not more than 250 ppm, such as not more than 125 ppm, such as not more than 100 ppm, based on the total weight of the cleaner-coat applicator composition. Lithium can be present in the cleaner-coat applicator composition in an amount of 2 ppm to 1,000 ppm, such as 5 ppm to 500 ppm, such as 5 ppm to 250 ppm, such as 25 ppm to 125 ppm, such as 75 ppm to 125 ppm, such as 75 ppm to 100 ppm, based on the total weight of the cleaner-coat applicator composition.

[0067] The cleaner-coat applicator composition can optionally comprise molybdenum. The lithium source in the cleaner-coat applicator composition can be in the form of a salt. Non-limiting examples of suitable molybdenum salts include sodium molybdate, lithium molybdate, calcium molybdate, potassium molybdate, ammonium molybdate, molybdenum chloride, molybdenum acetate, molybdenum sulfamate, molybdenum formate, molybdenum lactate, and combinations thereof.

[0068] Molybdenum can be present in the cleaner-coatant composition in an amount of at least 5 ppm, such as at least 25 ppm, such as at least 50 ppm, such as at least 100 ppm, based on the total weight of the cleaner-coatant composition. Molybdenum can be present in the cleaner-coatant composition in an amount of not more than 5,000 ppm, such as not more than 2,500 ppm, such as not more than 500 ppm, such as not more than 250 ppm, such as not more than 150 ppm, based on the total weight of the cleaner-coatant composition. Molybdenum can be present in the cleaner-coatant composition in an amount of 5 ppm to 5,000 ppm, such as 25 ppm to 2,500 ppm, such as 50 ppm to 500 ppm, such as 25 ppm to 250 ppm, such as 100 ppm to 150 ppm, based on the total weight of the cleaner-coatant composition.

[0069] The cleaner-coatant composition can include a pH of at least 1.0, such as at least 1.5, such as at least 2.0, such as at least 3.0, such as at least 3.5, such as at least 4.0. The cleaner-coatant composition can include a pH of not more than 6.0, such as not more than 5.5, such as not more than 5.0, such as not more than 4.5, such as not more than 3.5. The cleaner-coatant composition can include a pH of 1.0 to 6.0, such as 1.5 to 6.0, such as 2.0 to 5.0, such as 3.0 to 5.0, such as 1.0 to 5.0, such as 1.5 to 4.5, such as 2.0 to 3.5, such as 4.0 to 6.0, such as 4.0 to 5.5, such as 4.0 to 5.0. The pH described herein can be measured using a pH meter (Orion® DualStar pH / ISE Dual Channel Benchtop Meter, available from ThermoFisher Scientific, Waltham, MA, USA) and a pH probe (Fisher Scientific ACCUMET pH Probe (Ag / AgCl Reference Electrode)) at ambient conditions. The pH of the cleaner-coatant composition can be maintained by inclusion of an acidic material, including water-soluble and / or water-dispersible acids, such as nitric acid, sulfuric acid, and / or phosphoric acid. The pH of the cleaner-coatant composition can be maintained by inclusion of a basic material, including water-soluble and / or water-dispersible bases, such as sodium hydroxide, sodium carbonate, potassium hydroxide, ammonium hydroxide, ammonia, and / or amines (such as triethylamine, methylethylamine), or mixtures thereof.

[0070] In some cases, the cleaner-coat composition can not include phosphate ions or phosphate-containing compounds and / or the formation of sludge formed in the use of zinc phosphate-based treatments, such as aluminum phosphate, iron phosphate, and / or zinc phosphate. As used herein, "phosphate-containing compounds" include compounds containing elemental phosphorous, such as orthophosphates, pyrophosphates, metaphosphates, tripolyphosphates, and the like, and can include, but are not limited to, monovalent, divalent, or trivalent cations, such as: sodium, potassium, calcium, zinc, nickel, manganese, aluminum, and / or iron. When the composition and / or the coating deposited on the substrate surface by depositing the cleaner-coat composition is substantially free, essentially free, or completely free of phosphate, this includes phosphate ions or any form of phosphate-containing compounds.

[0071] Thus, the cleaner-coat composition and / or the coating deposited on the substrate surface by depositing the cleaner-coat composition can be substantially free, or in some cases can be essentially free, or in some cases can be completely free of one or more of any of the ions or compounds listed in the previous paragraph. A cleaner-coat composition and / or coating that is substantially free of phosphate means that phosphate ions or phosphate-containing compounds are not intentionally added, but can be present in trace amounts, such as due to impurities or unavoidable contamination from the environment. In other words, the amount of material is so small that it does not affect the properties of the composition. This can further encompass that the phosphates are not present in the cleaner-coat composition and / or the deposited material at such levels that they cause a burden to the environment. The term "substantially free" means that the cleaner-coat composition and / or the coating contains less than 5 ppm of any or all of the phosphate anions or compounds listed in the previous paragraph, if any, based on the total weight of the composition or the deposited material, respectively. The term "essentially free" means that the cleaner-coat composition and / or the coating contains less than 1 ppm of any or all of the phosphate anions or compounds listed in the previous paragraph. The term "completely free" means that the cleaner-coat composition and / or the coating contains less than 1 ppb of any or all of the phosphate anions or compounds listed in the previous paragraph, if any.

[0072] The cleaner-applicator composition can not include chromium or chromium-containing compounds. That is, the cleaner-applicator composition and / or the coating deposited from the cleaner-applicator composition can be substantially free, can be essentially free, and / or can be completely free of such chromium or chromium-containing compounds. As used herein, the term "chromium-containing compounds" refers to materials that include trivalent and / or hexavalent chromium. Non-limiting examples of such materials include chromic acid, chromium trioxide, chromic anhydride, dichromates such as ammonium dichromate, sodium dichromate, potassium dichromate, and calcium dichromate, barium dichromate, magnesium dichromate, zinc dichromate, cadmium dichromate, strontium dichromate, chromium (III) sulfate, chromium (III) chloride, and chromium (III) nitrate. When the cleaner-applicator composition or the coating deposited from the cleaner-applicator composition is substantially free, essentially free, or completely free of chromium, this includes chromium in any form, such as but not limited to the trivalent and hexavalent chromium-containing compounds listed above.

[0073] Thus, optionally, the cleaner-applicator composition and / or the coating can be substantially free, can be essentially free, and / or can be completely free of one or more of any of the elements or compounds listed in the preceding paragraph. A cleaner-applicator composition or coating that is substantially free of chromium or derivatives thereof means that chromium or derivatives thereof is not intentionally added, but can be present in trace amounts, such as due to impurities or unavoidable contamination from the environment. In other words, the amount of the material is so small that it does not affect the properties of the cleaner-applicator composition or coating. In the case of chromium, this can further include that its elements or compounds are not present in the cleaner-applicator composition and / or coating at such levels that they pose a burden to the environment. The term "substantially free" means that the cleaner-applicator composition and / or coating contains less than 10 ppm of any or all of the elements or compounds listed in the preceding paragraph, if any, based on the total weight of the composition or coating, respectively. The term "essentially free" means that the cleaner-applicator composition and / or coating contains less than 1 ppm of any or all of the elements or compounds listed in the preceding paragraph, if any. The term "completely free" means that the cleaner-applicator composition and / or coating includes 0 ppm of such materials, or that such materials are below the detection limit of common analytical techniques.

[0074] The cleaner-applicator composition can include an aqueous medium, and can optionally contain other materials such as adjuvants conventionally used in the art of pretreatment compositions. In the aqueous medium, there can be a water-dispersible organic solvent, for example, an alcohol having up to about 8 carbon atoms, such as methanol, isopropanol, and the like; or a glycol ether, such as a monoalkyl ether of ethylene glycol, diethylene glycol, or propylene glycol, and the like. When present, the water-dispersible organic solvent is typically used in an amount of up to about ten percent by volume, based on the total volume of the aqueous composition.

[0075] The cleaner-coating composition can also include a resinous binder. Suitable resins include the reaction product of one or more alkanolamines and an epoxy-functional material containing at least two epoxy groups, such as the reaction products disclosed in U.S. Patent No. 5,653,823. In some cases, such resins contain beta hydroxyl ester, imide or sulfide functionality incorporated by using dimethylol propionic acid, phthalimide or mercaptoglycerine as additional reactants in the resin preparation. Alternatively, the reaction product is a diglycidyl ether of bisphenol A (commercially available, for example, as EPON 880 from Shell Chemical Company), a reaction product of dimethylol propionic acid and diethanolamine in a molar ratio of 0.6 to 5.0:0.05 to 5.5:1. Other suitable resinous binders include: water-soluble and water-dispersible polyacrylic acids, as disclosed in U.S. Patent Nos. 3,912,548 and 5,328,525; phenol-formaldehyde resins, as described in U.S. Patent No. 5,662,746; water-soluble polyamides, such as those disclosed in WO 95 / 33869; copolymers of maleic acid or acrylic acid with allyl ethers, as described in Canadian Patent Application 2,087,352; and water-soluble and water-dispersible resins, including epoxy resins, aminoplastics, phenol-formaldehyde resins, tannins and polyvinylphenols, as discussed in U.S. Patent No. 5,449,415.

[0076] The resinous binder can generally be present in the cleaner-coating composition in an amount of 0.005 to 30 weight percent, such as 0.5 to 3 weight percent, based on the total weight of the ingredients in the cleaner-coating composition.

[0077] The cleaner-coating composition can be substantially free or in some cases completely free of any resinous binder. As used herein, the term "substantially free" means that any resinous binder is present in the cleaner-coating composition in trace amounts of less than 0.005 weight percent when used in reference to the absence of a resinous binder in the cleaner-coating composition. As used herein, the term "completely free" means that no detectable resinous binder is present in the cleaner-coating composition.

[0078] The cleaner-coating composition can be substantially free, essentially free or completely free of sodium nitrobenzenesulfonate.

[0079] Electrodepositable coating compositions

[0080] As described above, the system for treating a substrate includes an electrodepositable coating composition.

[0081] As used herein, the term “electrodepositable coating composition” refers to a composition that is capable of being deposited onto an electrically conductive substrate under the influence of an applied electrical potential between two electrodes immersed in the electrodepositable coating composition, wherein one of the electrodes is the substrate to be coated.

[0082] The electrodepositable coating composition comprises an electrodepositable binder. For example, the electrodepositable binder can comprise an organic and / or inorganic electrodepositable binder. As used herein, the term “binder” refers to the non-volatile component of the electrodepositable coating composition, excluding fillers.

[0083] As used herein, an “organic” electrodepositable binder refers to a film-forming polymer having a backbone structure that includes carbon atoms in the backbone. As used herein, an “inorganic” electrodepositable binder refers to a film-forming polymer having a backbone structure that does not include carbon atoms in the backbone, such as a silicone-based material. It will be appreciated that the electrodepositable binder can also comprise a mixture of organic and inorganic film-forming and / or curing agent materials.

[0084] 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 coating layer upon reaction with a curing agent or crosslinking 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 effect curing of the coating composition to form a coating layer. As used herein, the term “cure,” “cured,” or similar terms mean that a portion of the coating composition is crosslinked to form a coating layer.

[0085] The electrodepositable coating composition can comprise an ionic salt group-containing film-forming polymer, such as a cationic salt group-containing film-forming polymer or an anionic salt group-containing film-forming polymer.

[0086] For example, the ionic salt group-containing film-forming polymer can comprise a reaction product of reactants comprising (a) a polyepoxide; (b) a difunctional chain extender; and (c) a monofunctional reactant. Non-limiting examples of such polymers are provided in paragraphs

[0023] to

[0038] of International Application No. PCT / US22 / 73356, the incorporated portions of which are incorporated herein by reference.

[0087] As used herein, the term "cationic salt group-containing film-forming polymer" refers to a polymer that includes at least partially neutralized cationic salt groups (such as amine, sulfonium, and / or ammonium salt groups) that impart a positive charge. The cationic salt group-containing film-forming polymer can include active hydrogen functional groups. As used herein, the term "active hydrogen functional group" refers to those functional groups that react with isocyanate and include, for example, hydroxyl groups, primary or secondary amine groups, carbamate, and thiol groups.

[0088] Non-limiting examples of polymers suitable for use as cationic salt group-containing film-forming polymers for electrodepositable coating compositions include, but are not limited to, alkyd resin polymers, acrylics, polyepoxides, polyamides, polyurethanes, polyureas, polyethers, and polyesters, and adducts, derivatives, and combinations thereof.

[0089] The cationic salt group-containing film-forming polymer can be made cationic and water- dispersible by at least partial neutralization with an acid such as formic acid, acetic acid, methanesulfonic acid, lactic acid, phosphoric acid, and / or sulfamic acid.

[0090] The degree of neutralization of the cationic salt group-containing film-forming polymer can vary depending on the particular polymer involved. However, sufficient acid should be used to neutralize the cationic salt group-containing film-forming polymer such that the cationic salt group-containing film-forming polymer can be dispersed in an aqueous dispersion medium. For example, the amount of acid used can provide at least 20% of the total theoretical neutralization. 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 cationic salt group-containing film-forming polymer can range between any combination of values, such as, for example, 20% or more, to, such as, for example, greater than 100%, inclusive of the recited values. For example, the total amount of acid used to neutralize the active hydrogen-containing, cationic salt group-containing film-forming polymer can be 20%, 35%, 50%, 60%, 80%, or 100% or greater, based on the total amines in the cationic salt group-containing film-forming polymer.

[0091] As used herein, the term "anionic salt group-containing film-forming polymer" refers to an anionic polymer that includes at least partially neutralized anionic functional groups (such as carboxylic acid groups and / or phosphoric acid groups) that impart a negative charge. The anionic salt group-containing film-forming polymer can include active hydrogen functional groups.

[0092] Non-limiting examples of polymers suitable for use as anionic salt group-containing film-forming polymers 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 including alkyd resins and amine-aldehydes, and adducts, derivatives, and combinations thereof.

[0093] Non-limiting examples of inorganic electrodepositable film-forming polymers include organosilicon-based film-forming polymers. Non-limiting examples of such polymers are described in paragraphs

[0007] to

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

[0094] The ionically salt group-containing film-forming polymer can be present in the electrodepositable coating composition in an amount of at least 40 weight percent, such as at least 50 weight percent, such as at least 55 weight percent, such as at least 60 weight percent, based on the total weight of resin solids of the electrodepositable coating composition. The ionically salt group-containing film-forming polymer can be present in the electrodepositable coating composition in an amount of not more than 90 weight percent, such as not more than 80 weight percent, such as not more than 75 weight percent, based on the total weight of resin solids of the electrodepositable coating composition. The ionically salt group-containing film-forming polymer can be present in the electrodepositable coating composition in an amount of 40 weight percent to 90 weight percent, such as 40 weight percent to 80 weight percent, such as 40 weight percent to 75 weight percent, such as 50 weight percent to 90 weight percent, such as 50 weight percent to 80 weight percent, such as 50 weight percent to 75 weight percent, such as 55 weight percent to 90 weight percent, such as 55 weight percent to 80 weight percent, such as 55 weight percent to 75 weight percent, such as 60 weight percent to 90 weight percent, such as 60 weight percent to 80 weight percent, such as 60 weight percent to 75 weight percent, based on the total weight of resin solids of the electrodepositable coating composition.

[0095] As used herein, “resin solids” include the ionically salt group-containing film-forming polymer, the curing agent, and any additional water-dispersible non-pigmented components present in the electrodepositable coating composition.

[0096] The electrodepositable coating compositions of the present disclosure can further include a curing agent. The curing agent can react with the reactive groups, such as active hydrogen groups, of the ionically salt group-containing film-forming polymer, as well as any reactive groups of any additional resin material, if present, to effect curing of the electrodepositable coating composition to form a coating layer. Non-limiting examples of suitable curing agents include at least partially or completely blocked polyisocyanates, as well as aminoplast resins and / or phenoplast resins, such as phenol formaldehyde condensates, including allyl ethers and / or derivatives thereof.

[0097] As used herein, “blocked polyisocyanate” means a polyisocyanate in which at least a portion of the isocyanate groups are blocked with a blocking group introduced by reaction of a free isocyanate group of the polyisocyanate with a blocking agent. “Blocked” means that the isocyanate groups have reacted with a blocking agent such that the resulting blocked isocyanate groups are stable to active hydrogens at ambient temperature, e.g., room temperature (23°C). The 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 reactive groups, such as active hydrogen groups, of the ion-containing salt group-containing film-forming polymer to effect curing of the coating composition and formation of a coating.

[0098] The blocking agent that dissociates from the blocked polyisocyanate curing agent during curing can be removed from the coating by volatilization. Alternatively, at least a portion of the blocking agent can remain in the coating after curing.

[0099] 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, non-limiting examples of 1,2 polyols are provided in paragraphs

[0022] to

[0035] of International Publication No. WO 2021 / 138583 A1, the cited portions of which are incorporated herein by reference.

[0100] Non-limiting examples of blocked polyisocyanates comprising blocking groups derived from blocking agents comprising a- hydroxy amides, esters, or thioesters, and optionally a second blocking agent are provided in paragraphs

[0010] to

[0029] of International Publication No. WO 2018 / 148306 A1, the cited portions of which are incorporated herein by reference. The blocked polyisocyanate can be a fully blocked polyisocyanate in which substantially 100% of the isocyanate groups of the polyisocyanate are blocked with one or more blocking groups. Optionally, the blocked polyisocyanate curing agent can be an at least partially blocked polyisocyanate having less than 100% of the isocyanate groups blocked, so long as the coating composition maintains a stable dispersion.

[0101] The at least partially blocked polyisocyanate can be partially blocked with one or more blocking groups discussed above, in which the remaining isocyanate groups are reacted with the polymer backbone, such as described in U.S. Patent No. 3,947,338, column 2, line 65 to column 5, line 33, the cited portions of which are incorporated herein by reference.

[0102] The capped polyisocyanate curing agent can 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-triazine, and any combination thereof.

[0103] The curing agent can include an aminoplast resin or a phenoplast resin. Aminoplast resins are condensation products of aldehydes with substances bearing amino or amido groups. Phenoplast resins are formed by condensation of aldehyde and phenol.

[0104] Non-limiting examples of commercially available aminoplast resins include those available under the trademarks Cymel® from Allnex Belgium SA / NV (such as Cymel 1130 and 1156) and Resimene® from INEOS Melamines (such as 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, through column 17, line 47, which portion of the '679 patent is hereby incorporated by reference. As disclosed in the foregoing portion of the '679 patent, aminoplasts can be used in combination with methylene phenol ethers. Non-limiting examples of commercially available aminoplast resins include those available under the trademarks Cymel® from Allnex Belgium SA / NV (such as Cymel 1130 and 1156) and Resimene® from INEOS Melamines (such as 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, through column 17, line 47, which portion of the '679 patent is hereby incorporated by reference. As disclosed in the foregoing portion of the '679 patent, aminoplasts can be used in combination with methylene phenol ethers.

[0105] Suitable aminoplast resins and phenoplast resins are further described in U.S. Patent No. 4,812,215 at column 6, line 20, through column 7, line 12, the referenced portion of which patent is incorporated herein by reference.

[0106] Non-limiting examples of additional curing agents include silicone-based curing agents. Non-limiting examples of such curing agents are in paragraphs

[0030] to

[0043] of International Publication No. WO 2021 / 138384 Al, the referenced portion of which publication is incorporated herein by reference.

[0107] ​The curing agent can be present in the electrodepositable coating composition in an amount of at least 10 percent by weight, such as at least 20 percent by weight, such as at least 25 percent by weight, based on the total weight of resin solids of the electrodepositable coating composition. The curing agent can be present in the electrodepositable coating composition in an amount of not more than 60 percent by weight, such as not more than 50 percent by weight, such as not more than 45 percent by weight, such as not more than 40 percent by weight, based on the total weight of resin solids of the electrodepositable coating composition. The curing agent can be present in the electrodepositable coating composition in an amount of 10 percent by weight to 60 percent by weight, such as 10 percent by weight to 50 percent by weight, such as 10 percent by weight to 45 percent by weight, such as 10 percent by weight to 40 percent by weight, such as 20 percent by weight to 60 percent by weight, such as 20 percent by weight to 50 percent by weight, such as 20 percent by weight to 45 percent by weight, such as 20 percent by weight to 40 percent by weight, such as 25 percent by weight to 60 percent by weight, such as 25 percent by weight to 50 percent by weight, such as 25 percent by weight to 45 percent by weight, such as 25 percent by weight to 40 percent by weight, based on the total weight of resin solids of the electrodepositable coating composition.

[0108] The electrodepositable coating composition further comprises a curing catalyst. As used herein, the term "curing catalyst" is used interchangeably with "catalyst" and refers to a substance that increases the rate or lowers the activation energy of a chemical reaction without itself undergoing any permanent chemical change. For example, the catalyst can catalyze a carbamate exchange reaction, and in particular, catalyze the de-blocking of blocked polyisocyanate blocking groups.

[0109] Non-limiting examples of curing catalysts include: amine-containing compounds; compounds or complexes of metals such as tin, bismuth, cerium, zinc, and / or titanium; and combinations thereof.

[0110] Catalysts suitable for use in cationic electrodepositable coating compositions include, but are not limited to, metal oxides (e.g., oxides of cerium, zirconium, and bismuth) and salts thereof; compounds or complexes of zinc; and / or cyclic guanidines, such as the cyclic guanidines described in U.S. Patent No. 7,842,762, col. 1, line 53 to col. 4, line 18 and col. 16, line 62 to col. 19, line 8, the incorporated references of which are incorporated herein by reference.

[0111] 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 that are typically activated by heat. Non-limiting examples of latent acid catalysts are listed 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.

[0112] The amine-containing curing catalyst can 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.

[0113] Non-limiting examples of suitable guanidine curing catalysts are provided in paragraphs

[0039] to

[0050] of International Publication No. WO 2018 / 0172519 Al, the cited portions of which are incorporated herein by reference.

[0114] Non-limiting examples of imidazole curing catalysts are described in paragraphs

[0062] to

[0108] of U.S. Publication No. 2022 / 0154014 Al, the cited portions of which are incorporated herein by reference.

[0115] Non-limiting examples of amidine curing catalysts can include 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0116] The zinc-containing catalyst can include a metal salt and / or complex of zinc such as, but not limited to, a zinc (II) amidinate complex, zinc octoate, zinc naphthenate, zinc tallate, a carboxylate of zinc having 8 to 14 carbons in the carboxylate group, zinc acetate, zinc sulfonate, zinc methylsulfonate, or any combination thereof. The zinc (II) amidinate complex can contain an amidinate and a carboxylate ligand.

[0117] The curing catalyst can include a bismuth catalyst. Non-limiting examples of bismuth curing catalysts and their amounts of use are provided in paragraphs

[0036] to

[0050] of International Publication No. WO 2021 / 138583 Al, the cited portions of which are incorporated herein by reference.

[0118] The curing catalyst can include a compound and / or complex of titanium 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 where R 1 is a n-butyl group such as tetrabutyl titanate.

[0119] The cure catalysts can be present in the electrodepositable coating composition in any suitable amount. For example, the amine and / or zinc-containing cure catalysts 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 total weight of the resin solids of the coating composition. The amine and / or zinc-containing cure catalysts 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.%, based on the total weight of the resin solids of the coating composition. The amine and / or zinc-containing cure catalysts can be present in the coating composition in an amount of 0.1 to 7 wt.%, such as 0.1 to 4 wt.%, such as 0.1 to 2 wt.%, such as 0.1 to 1.5 wt.%, such as 0.1 to 1 wt.%, such as 0.2 to 7 wt.%, such as 0.2 to 4 wt.%, such as 0.2 to 2 wt.%, such as 0.2 to 1.5 wt.%, such as 0.2 to 1 wt.%, such as 0.5 to 7 wt.%, such as 0.5 to 4 wt.%, such as 0.5 to 2 wt.%, such as 0.5 to 1.5 wt.%, such as 0.5 to 1 wt.%, such as 0.8 to 7 wt.%, such as 0.8 to 4 wt.%, such as 0.8 to 2 wt.%, such as 0.8 to 1.5 wt.%, such as 0.8 to 1 wt.%, such as 1 to 7 wt.%, such as 1 to 4 wt.%, such as 1 to 2 wt.%, such as 1 to 1.5 wt.%, such as 1.5 to 7 wt.%, such as 1.5 to 4 wt.%, such as 1.5 to 2 wt.%, based on the total weight of the resin solids of the coating composition.

[0120] The electrodepositable coating composition can be substantially free, essentially 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 wt.%, based on the total weight of the electrodepositable coating composition. As used herein, an electrodepositable coating composition is "substantially free" of catalytic tin if the catalytic tin is present in an amount of less than 0.01 wt.%, based on the total weight of the electrodepositable coating composition. As used herein, an electrodepositable coating composition is "essentially free" of catalytic tin if the catalytic tin is present in an amount of less than 0.001 wt.%, based on the total weight of the electrodepositable coating composition.

[0121] The electrodepositable coating composition can optionally further comprise a polymer comprising at least one phosphated group. The polymer is not limited. Non-limiting examples of the polymer include addition polymers comprising at least one phosphated group, phosphated epoxy resins, and other polymers comprising at least one phosphated group.

[0122] The polymer can have a phosphoric acid equivalent weight of at least 0.01 milliequivalents per gram of polymer, such as at least 0.05, such as at least 0.1, such as at least 1, such as at least 2, such as at least 4. The polymer can have a phosphoric acid equivalent weight of not more than 10 milliequivalents per gram of polymer, such as not more than 7, such as not more than 5, such as not more than 3, such as not more than 2, such as not more than 1. The polymer can have a phosphoric acid equivalent weight of 0.01 to 10 milliequivalents per gram of polymer, such as 0.01 to 7, such as 0.01 to 5, such as 0.01 to 3, such as 0.01 to 2, such as 0.01 to 1, such as 0.05 to 10, such as 0.05 to 7, such as 0.05 to 5, such as 0.05 to 3, such as 0.05 to 2, such as 0.05 to 1, such as 0.1 to 10, such as 0.1 to 7, such as 0.1 to 5, such as 0.1 to 3, such as 0.1 to 2, such as 0.1 to 1, such as 1 to 10, such as 1 to 7, such as 1 to 5, such as 1 to 3, such as 1 to 2, such as 2 to 10, such as 2 to 7, such as 2 to 5, such as 2 to 3, such as 4 to 10, such as 4 to 7, such as 4 to 5. The phosphoric acid equivalent weight can be determined by dividing the total weight of the polymer by the total number of phosphoric acid groups present in the polymer.

[0123] As used herein, the terms “phosphated group” and “phosphoric acid group” refer to a phosphate radical group attached to a polymer. As used herein, “phosphate” refers to an anion derived from phosphoric acid having the general chemical formula [PO4] 3- , [HPO4] 2- , and / or [H2PO4] - . While reference is made herein to “phosphate” ions, derivatives of other phosphoric acid derivatives are within the scope of the present disclosure. Thus, unless otherwise specified, a phosphate ion can refer to a phosphonate anion derived from a phosphonic acid having the general chemical formula [RPO3] 2- , and / or [RHPO3] 1- ; and a phosphinate anion derived from a phosphinic acid.

[0124] The polymer comprising at least one phosphated group can include an addition polymer.

[0125] As used herein, the term "addition polymer" refers to a polymerization product formed from the polymerization of monomers that make up a monomer composition to form a polymer. After the monomers of the monomer composition are polymerized, the addition polymer contains structural units corresponding to the residue of each polymerized monomer. As used herein, the term "residue of" when referring to the composition of a polymer refers to the individual molecular units (i.e., structural units) in the polymer that result from the combination (i.e., reaction) of monomers during polymerization. Addition polymers are formed by polymerizing a monomer composition that includes ethylenically unsaturated monomers.

[0126] The monomer composition includes a phosphonic acid functional monomer. The phosphonic acid group can include a phosphonic acid group, a phosphinic acid group, or a combination thereof, as well as salts thereof. The phosphonic acid functional ethylenically unsaturated monomer can be a phosphonic acid dihydrogen ester of an alcohol, where the alcohol contains or is substituted with a polymerizable vinyl or ethylenic group. Suitable phosphonic acid functional ethylenically unsaturated monomers can include phosphoalkyl (meth)acrylates such as phosphoethyl (meth)acrylate, phosphopropyl (meth)acrylate, phosphobutyl (meth)acrylate, salts of phosphoalkyl (meth)acrylates, and mixtures thereof; CH2=C(R)—C(O)—O—(R p O) n —P(O)(OH)2, where R = H or CH3 and R p = alkyl, n is 1 to 20, such as SIPOMER PAM-100, SIPOMER PAM-200, SIPOMER PAM-300, and SIPOMER PAM-4000, all available from Solvay; phosphoalkoxy (meth)acrylates such as phosphoethyleneglycol (meth)acrylate, phosphodiethyleneglycol (meth)acrylate, phosphotriethyleneglycol (meth)acrylate, phosphopropylene glycol (meth)acrylate, phosphodipropylene glycol (meth)acrylate, phosphotripropylene glycol (meth)acrylate, salts thereof, and mixtures thereof. The phosphonic acid functional monomer can be present in the monomer composition in an amount of at least 0.1 wt.%, such as at least 1 wt.%, such as at least 2 wt.%, based on the total weight of the monomer composition. The phosphonic acid functional monomer can be present in the monomer composition in an amount of no more than 20 wt.%, such as no more than 10 wt.%, such as no more than 8 wt.%, based on the total weight of the monomer composition. The phosphonic acid functional monomer can be present in the monomer composition in an amount of 0.1 wt.% to 20 wt.%, such as 0.1 wt.% to 10 wt.%, such as 0.1 wt.% to 8 wt.%, such as 1 wt.% to 20 wt.%, such as 1 wt.% to 10 wt.%, such as 1 wt.% to 8 wt.%, such as 2 wt.% to 20 wt.%, such as 2 wt.% to 10 wt.%, such as 2 wt.% to 8 wt.%, based on the total weight of the monomer composition.

[0127] The monomer composition and the resulting addition polymer can further comprise at least one other ethylenically unsaturated monomer. For example, the monomer composition and the resulting addition polymer can further comprise C1-C 18 alkyl(meth)acrylate monomers; hydroxy-functional (meth)acrylate monomers; vinyl aromatic compounds; monomers comprising two or more ethylenically unsaturated groups per molecule; (meth)acrylamide monomers; monoalkyl (meth)acrylamide monomers; dialkyl (meth)acrylamide monomers; and / or hydroxy-functional (meth)acrylamide monomers.

[0128] As used herein, “(meth)acrylate” or “(meth)acrylamide” and like terms encompass both acrylate and methacrylate or acrylamide and methacrylamide, respectively.

[0129] The electrodepositable coating composition can further comprise pigments. Non-limiting examples of pigments include, for example, iron oxide, lead oxide, strontium chromate, carbon black, coal dust, titanium dioxide, talc, barium sulfate, thermally conductive, electrically insulative filler materials, thermally conductive, electrically conductive filler materials, non-thermally conductive, electrically insulative filler materials, flame retardant pigments, and color pigments such as cadmium yellow, cadmium red, chromium yellow, and the like. As used herein, “electrically insulative filler” means a pigment, filler, or inorganic powder having a volume resistivity of at least 10 W.m, as measured according to ASTM D257, C611, or B193. As used herein, “electrically conductive filler” means a pigment, filler, or inorganic powder having a volume resistivity of less than 10 W.m, as measured according to ASTM D257, C611, or B193. As used herein, “thermally conductive filler” means a pigment, filler, or inorganic powder having a thermal conductivity of at least 5 W / m-K at 25°C, as measured according to ASTM D7984. As used herein, “non-thermally conductive filler” means a pigment, filler, or inorganic powder having a thermal conductivity of less than 5 W / m-K at 25°C, as measured according to ASTM D7984.

[0130] The pigments can include platelet-shaped pigments, such as inorganic platelet-shaped pigments.

[0131] The platelet-shaped pigments can be phyllosilicate pigments. As used herein, the term “phyllosilicate” refers to a group of minerals having silicate sheets with a basic structure based on interconnected SiO4 -4 tetrahedra with a six-membered ring of the basic structure extending outward in an infinite sheet with three of the four oxygens from each tetrahedron shared with other tetrahedra, resulting in a phyllosilicate having the basic structural unit of Si2O5 -2 . The phyllosilicate can include hydroxide ions and / or cations at the center of the tetrahedra, such as, for example, Fe +2 , Mg +2or Al +3 The ions form a cationic layer between the silicate sheets, where the cations can coordinate with the oxygen and / or hydroxyl ions of the silicate layers. The term "layered silicate pigment" refers to a pigment material that includes a layered silicate. Non-limiting examples of layered silicate pigments include mica, chlorite, serpentine, talc, and clay minerals. Clay minerals include, for example, kaolin. The platelet-like structure of layered silicate pigments tends to give the pigments a platy structure, but the pigments can be manipulated (such as by mechanical means) to have other particle structures. These pigments can or can not swell when exposed to a liquid medium, and can or can not have leachable components (e.g., ions that can be attracted into a liquid medium).

[0132] Platy pigments can include platy mica pigments, platy chlorite pigments, platy serpentine pigments, platy talc pigments, and / or platy clay pigments. Platy clay pigments can comprise, consist essentially of, or consist of kaolin.

[0133] Pigment components comprising platy pigments can have an average equivalent spherical diameter of at least 50 nm and up to 25 microns or more. Average equivalent spherical diameter can be determined using dynamic light scattering, such as using a SEDIGRAPH III PLUS particle size analyzer available from Micromeritics Instrument Corp. As platy particles, pigments generally have substantially opposed surfaces, and the particles generally exhibit an aspect ratio of the longest axis to the shortest axis of at least 2: 1, such as at least 4: 1, such as at least 6: 1, such as at least 8: 1, such as at least 10: 1 or more. For example, platy pigments can have an average equivalent spherical diameter of at least 50 nm, such as at least 0.2 microns, such as at least 0.4 microns, such as at least 0.6 microns, such as at least 1 micron, such as at least 2 microns, such as at least 3 microns, such as at least 4 microns, such as at least 5 microns. Platy pigments can have an average equivalent spherical diameter of no more than 25 microns, such as no more than 15 microns, such as no more than 10 microns, such as no more than 5 microns, such as no more than 3.5 microns, such as no more than 2.5 microns, such as no more than 1.9 microns, such as no more than 1.5 microns, such as no more than 1 micron.

[0134] The ratio of pigment to binder (P:B) as described in the present disclosure can refer to the weight ratio of pigment to binder in the electrodepositable coating composition. The ratio of pigment to binder (P:B) of the pigment to the electrodepositable binder can be at least 0.05:1, such as at least 0.1:1, such as at least 0.2:1, such as at least 0.3:1, such as at least 0.35:1, such as at least 0.4:1, such as at least 0.5:1, such as at least 0.6:1, such as at least 0.67, such as at least 0.7:1, such as at least 0.75:1, such as at least 1:1, such as at least 1.25:1, such as at least 1.5:1. The ratio of pigment to binder (P:B) of the pigment to the electrodepositable binder can be no more than 2:1, such as no more than 1.75:1, such as no more than 1.5:1, such as no more than 1.25:1, such as no more than 1:1, such as no more than 0.75:1, such as no more than 0.7:1, such as no more than 0.6:1, such as no more than 0.55:1, such as no more than 0.5:1, such as no more than 0.25:1. The ratio of pigment to binder (P:B) of the pigment to the electrodepositable binder can be from 0.05:1 to 2:1, such as from 0.05:1 to 1:1, such as from 0.05:1 to 0.75:1, such as from 0.05:1 to 0.7:1, such as from 0.05:1 to 0.6:1, such as from 0.05:1 to 0.55:1, such as from 0.05:1 to 0.5:1, such as from 0.05 to 0.25:1, such as from 0.1:1 to 2:1, such as from 0.1:1 to 1:1, such as from 0.1:1 to 0.75:1, such as from 0.1:1 to 0.7:1, such as from 0.1:1 to 0.6:1, such as from 0.1:1 to 0.55:1, such as from 0.1:1 to 0.5:1, such as from 0.1:1 to 0.25:1, such as from 0.2:1 to 2:1, such as from 0.2:1 to 1:1, such as from 0.2:1 to 0.75:1, such as from 0.2:1 to 0.7:1, such as from 0.2:1 to 0.6:1, such as from 0.2:1 to 0.55:1, such as from 0.2:1 to 0.5:1, such as from 0.2:1 to 0.25:1, such as from 0.3:1 to 2:1, 0.3:1 to 1:1, such as from 0.3:1 to 0.75:1, such as from 0.3:1 to 0.7:1, such as from 0.3:1 to 0.6:1, such as from 0.3:1 to 0.55:1, such as from 0.3:1 to 0.5:1, such as from 0.4:1 to 2:1, such as from 0.4:1 to 1.75:1, such as from 0.4:1 to 1.5:1, such as from 0.4:1 to 1.25:1, such as from 0.4:1 to 1:1, such as from 0.4:1 to 0.75:1, such as from 0.4:1 to 0.7:1, such as from 0.4:1 to 0.6:1, such as from 0.4:1 to 0.55:1, such as from 0.4:1 to 0.5:1, such as from 0.5:1 to 2:1, such as from 0.5:1 to 1.75:1, such as from 0.5:1 to 1.50:1, such as 0.5:1 to 1.25:1, such as 0.5:1 to 1:1, such as 0.5:1 to 0.75:1, such as 0.5:1 to 0.7:1, such as 0.5:1 to 0.6:1, such as 0.5:1 to 0.55:1, such as 0.6:1 to 2:1, such as 0.6:1 to 1.75:1, such as 0.6:1 to 1.5:1, such as 0.6:1 to 1.25:1, such as 0.6:1 to 1:1, such as 0.6:1 to 0.75:1, such as 0.6:1 to 0.7:1, such as 0.67:1 to 2:1, such as 0.67:1 to 1.75:1, such as 0.67:1 to 1.5:1, such as 0.67:1 to 1.25:1, such as 0.67:1 to 1:1, such as 0.67:1 to 0.75:1, such as 0.67:1 to 0.7:1, such as 0.7:1 to 2:1, such as 0.7:1 to 1.75:1, such as 0.7:1 to 1.5:1, such as 0.7:1 to 1.25:1, such as 0.7:1 to 1:1, such as 0.7:1 to 0.75:1, such as 0.75:1 to 2:1, such as 0.75:1 to 1.75:1, such as 0.75:1 to 1.5:1, such as 0.75:1 to 1.25:1, such as 0.75:1 to 1:1, such as 1:1 to 2:1, such as 1:1 to 1.75:1, such as 1:1 to 1.5:1, such as 1:1 to 1.25:1, such as 1.25:1 to 2:1, such as 1.25:1 to 1.75:1, such as 1.25:1 to 1.5:1, such as 1.5:1 to 2:1, such as 1.5:1 to 1.75:1.

[0135] The ratio of pigment to binder (P:B) of the inorganic platelet pigment to the electrodepositable binder can 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 ratio of pigment to binder (P:B) of the inorganic platelet pigment to the electrodepositable binder can be no more than 2: 1, such as no more than 1.75: 1, such as no more than 1.5: 1, such as no more than 1.25: 1, such as no more than 1: 1, such as no more than 0.75: 1, such as no more than 0.7: 1, such as no more than 0.6: 1, such as no more than 0.55: 1, such as no more than 0.5: 1. The ratio of pigment to binder (P:B) of the inorganic platelet pigment to the electrodepositable binder can be from 0.4: 1 to 2: 1, such as from 0.4: 1 to 1.75: 1, such as from 0.4: 1 to 1.5: 1, such as from 0.4: 1 to 1.25: 1, such as from 0.4: 1 to 1: 1, such as from 0.4: 1 to 0.75: 1, such as from 0.4: 1 to 0.7: 1, such as from 0.4: 1 to 0.6: 1, such as from 0.4: 1 to 0.55: 1, such as from 0.4: 1 to 0.5: 1, such as from 0.5: 1 to 2: 1, such as from 0.5: 1 to 1.75: 1, such as from 0.5: 1 to 1.50: 1, such as from 0.5: 1 to 1.25: 1, such as from 0.5: 1 to 1: 1, such as from 0.5: 1 to 0.75: 1, such as from 0.5: 1 to 0.7: 1, such as from 0.5: 1 to 0.6: 1, such as from 0.5: 1 to 0.55: 1, such as from 0.6: 1 to 2: 1, such as from 0.6: 1 to 1.75: 1, such as from 0.6: 1 to 1.5: 1, such as from 0.6: 1 to 1.25: 1, such as from 0.6: 1 to 1: 1, such as from 0.6: 1 to 0.75: 1, such as from 0.6: 1 to 0.7: 1, such as from 0.75: 1 to 2: 1, such as from 0.75: 1 to 1.75: 1, such as from 0.75: 1 to 1.5: 1, such as from 0.75: 1 to 1.25: 1, such as from 0.75: 1 to 1: 1, such as from 1: 1 to 2: 1, such as from 1: 1 to 1.75: 1, such as from 1: 1 to 1.5: 1, such as from 1: 1 to 1.25: 1, such as from 1.25: 1 to 2: 1, such as from 1.25: 1 to 1.75: 1, such as from 1.25: 1 to 1.5: 1, such as from 1.5: 1 to 2: 1, such as from 1.5: 1 to 1.75: 1.

[0136] The electrodepositable coating composition can optionally include a dispersant to aid in the dispersion of the pigment and other optional filler materials.

[0137] The electrodepositable coating and / or the electrodepositable composition can optionally include a corrosion inhibitor. Any suitable corrosion inhibitor can be used. For example, the corrosion inhibitor can include a corrosion inhibitor containing yttrium, lanthanum, cerium, calcium, azoles, or any combination thereof.

[0138] Non-limiting examples of suitable azoles include benzotriazole, 5-methylbenzotriazole, 2-aminothiazole, and salts thereof.

[0139] The corrosion inhibitor, if any, can be present in the electrodepositable coating composition in an amount of at least 0.001 wt.%, such as at least 5 wt.%, based on the total weight of the electrodepositable coating composition. The corrosion inhibitor, if any, can be present in the electrodepositable coating composition in an amount of no more than 25 wt.%, such as no more than 15 wt.%, such as no more than 10 wt.%, based on the total weight of the electrodepositable coating composition. The corrosion inhibitor, if any, can be present in the electrodepositable coating composition in an amount of 0.001 wt.% to 25 wt.%, such as 0.001 wt.% to 15 wt.%, such as 0.001 wt.% to 10 wt.%, such as 5 wt.% to 25 wt.%, such as 5 wt.% to 15 wt.%, such as 5 wt.% to 10 wt.%, based on the total weight of the electrodepositable coating composition.

[0140] Alternatively, the electrodepositable coating composition can be substantially free, essentially free, or completely free of a corrosion inhibitor.

[0141] According to the present disclosure, the electrodepositable coating composition can include other optional ingredients, such as various additives, including fillers, plasticizers, antioxidants, biocides, UV light absorbers and stabilizers, hindered amine light stabilizers, antifoams, fungicides, dispersion aids, flow control agents, surfactants, wetting agents, or combinations thereof. Alternatively, the electrodepositable coating composition can be completely free of any optional ingredients, i.e., the optional ingredients are not present in the electrodepositable coating composition. The other additives mentioned above can be present in the electrodepositable coating composition cumulatively or separately in an amount of 0.01 wt.% to 3 wt.%, based on the total weight of the resin solids of the electrodepositable coating composition.

[0142] According to the present disclosure, the electrodepositable coating composition can include water and / or one or more organic solvents. Water can be present, for example, in an amount of 40 to 90 weight percent, such as 50 to 75 weight percent, based on the total weight of the electrodepositable coating composition. Examples of suitable organic solvents include oxygen-containing 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 monoethyl and monobutyl ethers of these glycols. Examples of other at least partially water-miscible solvents include alcohols, such as ethanol, isopropanol, butanol, and diacetone alcohol. If used, the organic solvent can generally be present in an amount of less than 10 weight percent, such as less than 5 weight percent, based on the total weight of the electrodepositable coating composition. The electrodepositable coating composition can specifically be provided in the form of a dispersion, such as an aqueous dispersion.

[0143] According to the present disclosure, the electrodepositable coating composition can have a total solids content of at least 1 weight percent, such as at least 5 weight percent, and can be no more than 50 weight percent, such as no more than 40 weight percent, such as no more than 20 weight percent, based on the total weight of the electrodepositable coating composition. The electrodepositable coating composition can have a total solids content of 1 to 50 weight percent, such as 5 to 40 weight percent, such as 5 to 20 weight percent, 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., material that will not volatilize when heated to 110°C for 15 minutes.

[0144] The electrodepositable coating composition can be electrocoated onto a conductive substrate by electrophoresis and at least partially cured using coating conditions, times, and temperatures as known to those skilled in the art.

[0145] The cationic electrodepositable coating composition of the present disclosure can be deposited on a conductive substrate by placing the composition in contact with a conductive cathode and a conductive anode, with the surface to be coated being the cathode. Upon contact with the composition, an adherent coating of the coating composition can be deposited on the cathode when a sufficient voltage is applied between the electrodes.

[0146] The anionic electrodepositable coating composition of the present disclosure can be deposited on a conductive substrate by placing the composition in contact with a conductive cathode and a conductive anode, with the surface to be coated being the anode. Upon contact with the composition, an adherent coating of the coating composition can be deposited on the anode when a sufficient voltage is applied between the electrodes.

[0147] In electrophoretic applications of the electrodepositable coating compositions of the present disclosure, the applied voltage can vary and can be, for example, as low as one volt to as high as several thousand volts, such as between 50 volts and 500 volts. The current density can be, for example, between 0.5 and 15 amperes per square foot, and tends to decrease during electrodeposition, which is indicative of the formation of an insulating coating.

[0148] Pre-spray compositions

[0149] As previously mentioned, the system for treating a substrate can include a pre- spray composition. The pre-spray composition can include, consist essentially of, or consist of a surfactant and a binder and optionally water.

[0150] The surfactant can be any of the surfactants disclosed above. The surfactant can be present in the pre-spray composition in an amount of at least 50 ppm, such as at least 100 ppm, such as at least 200 ppm, such as at least 500 ppm, based on the total weight of the pre-spray composition. The surfactant can be present in the pre-spray composition in an amount of not more than 20,000 ppm, such as not more than 10,000 ppm, such as not more than 7,500 ppm, such as not more than 5,000 ppm, based on the total weight of the pre-spray composition. The surfactant can be present in the pre-spray composition in an amount of 50 ppm to 20,000 ppm, such as 100 ppm to 10,000 ppm, such as 200 ppm to 7,500 ppm, such as 500 ppm to 5,000 ppm, based on the total weight of the pre-spray composition.

[0151] The builder can inhibit or reduce flash rust. The builder can include any of the builders disclosed above. The builder can optionally include sodium tripolyphosphate.

[0152] The builder can be present in the pre-spray composition in an amount of at least 5 ppm, such as at least 10 ppm, such as at least 50 ppm, based on the total weight of the pre- spray composition. The builder can be present in the pre-spray composition in an amount of not more than 2,000 ppm, such as not more than 1,500 ppm, such as not more than 1,000 ppm, based on the total weight of the pre-spray composition. The builder can be present in the pre-spray composition in an amount of 5 ppm to 5,000 ppm, such as 20 ppm to 2,000 ppm, such as 50 ppm to 1,000 ppm, based on the total weight of the pre-spray composition.

[0153] The pre-spray composition can have a pH of at least 1, such as at least 2, such as at least 2.5, such as at least 5. The pre-spray composition can have a pH of not more than 8.5, such as not more than 8, such as not more than 7.5. The pre-spray composition can have a pH of from 1 to 8.5, such as from 2 to 8, such as from 2.5 to 7.5, such as from 5 to 7.5.

[0154] The pre-spray composition can be substantially free, essentially free, or completely free of phosphates and / or chromium, details of which are described above.

[0155] The pre-spray composition can comprise an aqueous medium, an organic medium, or a combination thereof. Examples of organic media include, but are not limited to, glycol ethers and / or high flash point hydrocarbon solvents.

[0156] In examples, the solution or dispersion of the pre-spray composition can be applied to or contacted with the surface of the substrate by any conventional means known in the art. For example, the solution or dispersion can be contacted with the substrate by any of a variety of known techniques, such as dipping or immersion, spraying, intermittent spraying, spraying after dipping, dipping after spraying, brushing, or rolling. The solution or dispersion can be at a temperature ranging from 10 °C to 90 °C, such as from 25 °C to 75 °C, when applied to the metal substrate. For example, the process can be carried out at ambient or room temperature. The contact time is typically from 5 seconds to 5 minutes, such as from 10 seconds to 2 minutes.

[0157] Method

[0158] The present disclosure further relates to a method for coating a substrate, the method comprising applying any of the cleaner-coat compositions disclosed herein to at least a portion of a surface of the substrate.

[0159] The present disclosure further relates to a method of treating a substrate, the method comprising applying any of the cleaner-coat compositions disclosed herein and any of the electrodepositable coating compositions disclosed herein.

[0160] The substrate can be contacted with the cleaner-coat composition prior to being contacted with the electrodepositable coating composition.

[0161] The method can optionally further comprise a rinsing step between applying the cleaner-coat composition and applying the electrodepositable coating composition. Alternatively, the method can not comprise a rinsing step between applying the cleaner-coat composition and applying the electrodepositable coating composition.

[0162] The method of treating a substrate can optionally further comprise treating the substrate with any of the pre-spray compositions disclosed herein. The method can not comprise a rinsing step between applying the pre-spray composition and applying the cleaner-coat composition.

[0163] The substrate can be contacted with the pre-spray composition prior to contact with the cleaner-coat composition. The substrate can be contacted with the cleaner-coat composition prior to contact with the electrodepositable coating composition.

[0164] The solution or dispersion of the cleaner-coat composition can be applied to or contacted with the substrate surface spontaneously. For example, the solution or dispersion can be contacted with the substrate by any of a variety of known techniques, such as dipping or immersion, spraying, intermittent spraying, dipping followed by spraying, spraying followed by dipping, brushing, or rolling. The solution or dispersion can be at a temperature ranging from 20 °C to 50 °C, such as 25 °C to 40 °C, when applied to the metal substrate. For example, the process can be carried out at ambient or room temperature. The contact time is typically 15 seconds to 5 minutes, such as 30 seconds to 4 minutes, such as 1 minute to 3 minutes. As used herein, “spontaneously” or “spontaneous” when used in reference to the cleaner-coat composition means that the cleaner-coat composition is capable of reacting with and chemically altering the substrate surface without an externally applied voltage and bonding therewith to form a protective layer.

[0165] After the cleaner-coat composition is applied to at least a portion of the surface of the substrate, the substrate can optionally be rinsed with tap water, deionized water, and / or an aqueous solution of a rinsing agent to remove any residue. The wet substrate surface can be treated with one of the electrodepositable coating compositions described below, or the substrate can be dried prior to further treatment of the substrate surface, such as air drying, for example by using an air knife; by light distillation of water by briefly exposing the substrate to high temperatures (such as 15 °C to 100 °C, such as 20 °C to 90 °C) or in a heater assembly, for example using infrared heating, such as at 70 °C for 10 minutes; or by passing the substrate between squeeze rollers.

[0166] After application of the electrodepositable coating composition, the substrate can be heated to a temperature and for a time sufficient to at least partially cure the electrodepositable coating on the substrate. As used herein, the term "at least partially cured" means subjecting the coating composition to curing conditions such that at least a portion of the reactive groups of the components of the coating composition are cured or crosslinked to form a coating layer. Generally, the substrate can be heated to a temperature ranging from 250°F to 450°F (121.1°C to 232.2°C), such as 275°F to 400°F (135°C to 204.4°C), such as 300°F to 360°F (149°C to 180°C). For purposes of the present disclosure, all that is required is that the time be sufficient to effect curing of the coating on the substrate. The curing time can range, for example, from 10 minutes to 60 minutes, such as 20 to 40 minutes. The thickness of the resulting cured electrodeposited coating is not limited and can optionally range from 15 microns to 50 microns.

[0167] The method can optionally exclude the application of an additional cleaning composition that is not any of the compositions disclosed herein.

[0168] Substrate

[0169] The present disclosure also relates to a substrate that has been treated with one of the cleaner-coater compositions, systems, and / or methods disclosed herein.

[0170] Suitable substrates that can be used include metal substrates, metal alloy substrates, and / or metallized substrates, such as nickel-plated plastic. The metal or metal alloy can include or be steel, aluminum, zinc, nickel, and / or magnesium. For example, the steel substrate can be cold rolled steel, hot rolled steel, electrogalvanized steel, and / or hot-dipped galvanized steel. Aluminum alloys of the 1XXX, 2XXX, 3XXX, 4XXX, 5XXX, 6XXX, or 7XXX series, as well as clad aluminum alloys, can also be used as substrates. The aluminum alloy can include, for example, 0.01 wt. % copper to 10 wt. % copper. The aluminum alloy being treated can also include castings, such as 1XX.X, 2XX.X, 3XX.X, 4XX.X, 5XX.X, 6XX.X, 7XX.X, 8XX.X, or 9XX.X (e.g., A356.0). Magnesium alloys of the AZXX (including Eform Plus), AMXX, EVXX, ZEXX, ZCXX, HKXX, HZXX, QEXX, QHXX, WEXX, ZEK100, or Elektron 21 series can also be used as substrates. The substrates used can also include titanium and / or titanium alloys, zinc and / or zinc alloys, and / or nickel and / or nickel alloys. Suitable substrates for use in the present disclosure include those typically used in components of vehicle bodies (such as, but not limited to, doors, body panels, luggage compartment covers, roof panels, engine covers, roof and / or stringers, rivets, landing gear components, and / or skins used on aircraft), vehicle frames, vehicle parts, motorcycles, vehicle wheels, industrial structures and components, such as household appliances including washing machines, dryers, refrigerators, stoves, dishwashers, and the like, personal electronic products, agricultural equipment, lawn and garden equipment, metal fencing, guard rails, air conditioning units, heat pump units, heat exchangers, lawn furniture, and other articles. As used herein, “vehicle” or variations thereof includes, but is not limited to, civilian, commercial, and military aircraft and / or land vehicles, such as automobiles, motorcycles, trucks, and / or bicycles, including electric bicycles. The metal substrate can also be in the form of, for example, a metal sheet or a preformed part.

[0171] In examples, the substrate can be a multi-metallic article. As used herein, the term “multi-metallic article” means (1) an article having at least one surface comprising a first metal and at least one surface comprising a second metal different from the first metal, (2) a first article having at least one surface comprising a first metal and a second article having at least one surface comprising a second metal different from the first metal, or (3) both (1) and (2).

[0172] In examples, the substrate can include a battery or a battery component. The battery component can include, but is not limited to, a battery cell, a battery case, a battery module, a battery pack, a battery box, a battery cell housing, a battery pack housing, a battery cover and tray, a thermal management system, a battery enclosure, a module enclosure, a module support, a battery side plate, a battery cell jacket, a cooling module, a cooling tube, a cooling fin, a cooling plate, a bus bar, a battery frame, an electrical connector, a wire, or a copper or aluminum conductor or cable. The battery can be, for example, an electric vehicle battery, and the battery component can be, for example, an electric vehicle battery component.

[0173] In examples, the substrate can include a three-dimensional component formed by an additive manufacturing process such as selective laser melting, electron beam melting, directed energy deposition, binder jetting, metal extrusion, and the like. In examples, the three-dimensional component can be a metal and / or resin component.

[0174] The substrate can include a coating on at least a portion of a surface of the substrate. The coating can be formed from any of the cleaner-coat compositions disclosed herein. The coating can be formed from any of the electrodepositable coating compositions disclosed herein. The substrate can include a first coating formed from one of the cleaner-coat compositions disclosed herein on at least a portion of a surface of the substrate, and a second coating formed from one of the electrodepositable coating compositions disclosed herein on at least a portion of a surface of the substrate.

[0175] Additional coatings can be added to the substrate, including any suitable additional coatings known in the art, and each independently can be water-borne, solvent-borne, in the form of solid particulates (i.e., a powder coating composition), or in the form of a powder slurry. The additional coatings can each independently be cured, or optionally time and simultaneously cured in a “wet-on-wet” manner. As used herein, “wet-on-wet” refers to a process in which a coating (e.g., a clear coating) is applied over a different coating (e.g., a color coating) that is substantially uncured, and then both coatings are simultaneously cured.

[0176] The weight ratio of Group IVB metal to electropositive metal in a coating formed from one of the cleaner-coat compositions disclosed herein can be at least 1 : 10, such as at least 3:22, such as at least 1 :6. The weight ratio of Group IVB metal to electropositive metal in a coating formed from one of the cleaner-coat compositions disclosed herein can be no more than 2: 1, such as no more than 1 : 1, such as no more than 1 :2. The weight ratio of Group IVB metal to electropositive metal in a coating formed from one of the cleaner-coat compositions disclosed herein can be from 1 : 10 to 1 :2, such as from 3:22 to 1 : 1, such as from 1 :6 to 1 :2.

[0177] The coating formed from the cleaner-coat composition can include Group IVB metal in an amount of less than 50 mg / m2, such as from 3 mg / m2to 20 mg / m2, such as from 5 mg / m2to 15 mg / m2, as measured by ICP-OES. 2 2 2

[0178] The coating formed from the cleaner-coat composition can include electropositive metal in an amount of at least 5 mg / m2, such as from 10 mg / m2to 50 mg / m2, as measured by ICP-OES. 2

[0179] It has been surprisingly found that substrates treated with one of the cleaner-coat compositions disclosed herein exhibit lower Group IVB coating weights and improved corrosion performance compared to substrates treated with conventional cleaning compositions and conventional pretreatment compositions. Thus, the cleaner-coat compositions disclosed herein surprisingly provide improved corrosion performance using fewer processing steps. It has also been surprisingly found that substrates treated with one of the pre-spray compositions disclosed herein and one of the cleaner-coat compositions disclosed herein maintain corrosion performance compared to substrates treated with conventional cleaning compositions and conventional pretreatment compositions while allowing for the elimination of a rinsing step between application of the compositions.

[0180] Aspect

[0181] 1. A cleaner-coat composition comprising:

[0182] a Group IVB metal in an amount of from 50 ppm to 8,000 ppm based on the total weight of the cleaner-coat composition;

[0183] an electropositive metal, such as copper;

[0184] a builder comprising a phosphonate and / or a sugar alcohol; and ​​​​

[0185] a surfactant in an amount ranging from 50 ppm to 20,000 ppm, based on the total weight of the cleaner-coat composition.

[0186] 2. The cleaner-coat composition of aspect 1, wherein the Group IVB metal comprises zirconium, titanium, or a combination thereof, and wherein the Group IVB metal is optionally provided by hexafluorozirconic acid, hexafluorotitanic acid, a salt of either of the foregoing, or a combination of any of the foregoing.

[0187] 3. The cleaner-coat composition of aspect 1 or aspect 2, comprising the Group IVB metal in an amount ranging from:

[0188] (a) at least 100 ppm, such as at least 150 ppm, such as at least 200 ppm, such as at least 500 ppm, such as at least 600 ppm, such as at least 700 ppm, such as at least 800 ppm, such as at least 900 ppm, based on the total weight of the cleaner-coat composition;

[0189] (b) no more than 6,000 ppm, such as no more than 5,000 ppm, such as no more than 4,000 ppm, such as no more than 3,000 ppm, such as no more than 2,000 ppm, such as no more than 1,500 ppm, based on the total weight of the cleaner-coat composition; and / or

[0190] (c) from 100 ppm to 6,000 ppm, such as from 150 ppm to 4,000 ppm, such as from 200 ppm to 2,000 ppm, such as from 500 ppm to 5,000 ppm, such as from 500 ppm to 1,500 ppm, such as from 600 ppm to 4,000 ppm, such as from 700 ppm to 3,000 ppm, such as from 800 ppm to 2,000 ppm, such as from 900 ppm to 1,500 ppm, based on the total weight of the cleaner-coat composition.

[0191] 4. The cleaner-coat composition of any of the preceding aspects, comprising the positively charged metal in an amount ranging from:

[0192] (a) at least 2 ppm, such as at least 10 ppm, such as at least 20 ppm, based on the total weight of the cleaner-coat composition;

[0193] (b) no more than 200 ppm, such as no more than 100 ppm, such as no more than 75 ppm, such as no more than 40 ppm, based on the total weight of the cleaner-coat composition; and / or

[0194] (c) from 2 ppm to 200 ppm, such as from 2 ppm to 75 ppm, such as from 10 ppm to 200 ppm, such as from 20 ppm to 40 ppm, based on the total weight of the cleaner-coat composition.

[0195] 5. The cleaner-coat composition of any of the preceding aspects, wherein the phosphonate salt comprises a mono-phosphonate salt, a di-phosphonate salt such as etidronic acid, and / or a poly-phosphonate salt, and / or wherein the sugar alcohol comprises sorbitol.

[0196] 6. The system of any of the preceding aspects, wherein the builder comprises a flash rust inhibitor.

[0197] 7. The cleaner-coat composition of any of the preceding aspects, comprising the builder in an amount of:

[0198] (a) at least 10 ppm, such as at least 30 ppm, such as at least 50 ppm, based on the total weight of the cleaner-coat composition;

[0199] (b) no more than 2,500 ppm, such as no more than 2,000 ppm, such as no more than 1,500 ppm, based on the total weight of the cleaner-coat composition; and / or

[0200] (c) from 10 ppm to 2,500 ppm, such as from 30 ppm to 2,000 ppm, such as from 50 ppm to 1,500 ppm, based on the total weight of the cleaner-coat composition.

[0201] 8. The system of any of the preceding aspects, wherein the surfactant comprises a cationic surfactant, an anionic surfactant, a non-ionic surfactant, and / or an amphoteric surfactant.

[0202] 9. The cleaner-coat composition of any of the preceding aspects, comprising the surfactant in an amount of:

[0203] (a) at least 100 ppm, such as at least 200 ppm, such as at least 500 ppm, based on the total weight of the cleaner-coat composition;

[0204] (b) no more than 10,000 ppm, such as no more than 7,500 ppm, such as no more than 5,000 ppm, based on the total weight of the cleaner-coat composition; and / or

[0205] (c) from 100 ppm to 10,000 ppm, such as from 200 ppm to 7,500 ppm, such as from 500 ppm to 5,000 ppm, based on the total weight of the cleaner-coat composition.

[0206] 10. The cleaning agent-coating composition according to any one of the foregoing aspects, wherein the cleaning agent-coating composition is substantially free of, substantially free of, or completely free of phosphates and / or sodium nitrobenzenesulfonate.

[0207] 11. The cleaning agent-coating composition according to any one of the foregoing aspects, further comprising:

[0208] (a) Aqueous medium;

[0209] (b) Total fluoride, optionally in the following amounts:

[0210] (i) at least 60 ppm, such as at least 125 ppm, such as at least 200 ppm, such as at least 250 ppm, based on the total weight of the cleaning agent-coating composition;

[0211] (ii) based on the total weight of the cleaning agent-coating composition, not exceeding 10,000 ppm, such as not exceeding 7,500 ppm, such as not exceeding 5,000 ppm, such as not exceeding 3,000 ppm, such as not exceeding 2,500 ppm; and / or

[0212] (iii) 60 ppm to 10,000 ppm, such as 125 ppm to 7,500 ppm, such as 200 ppm to 5,000 ppm, such as 250 ppm to 2,500 ppm, based on the total weight of the cleaning agent-coating composition; and / or

[0213] (c) Free fluoride, optionally in the following amount:

[0214] (i) at least 25 ppm, such as at least 35 ppm, such as at least 50 ppm, based on the total weight of the cleaning agent-coating composition;

[0215] (ii) based on the total weight of the cleaning agent-coating composition, not exceeding 750 ppm, such as not exceeding 600 ppm, such as not exceeding 500 ppm; and / or

[0216] (iii) 25 ppm to 750 ppm, such as 35 ppm to 600 ppm, such as 50 ppm to 500 ppm, based on the total weight of the cleaning agent-coating composition.

[0217] 12. A system for processing a substrate, the system comprising:

[0218] The cleaning agent-coating composition according to any one of the foregoing aspects; and

[0219] An electrodepositable coating composition for at least partially coating the portion of the surface of the substrate treated with the cleaner-coater composition.

[0220] 13. A system for treating a substrate, the system comprising:

[0221] A cleaner-coater composition comprising: a Group IVB metal in an amount of 50 ppm to 8,000 ppm based on the total weight of the cleaner-coater composition; a positively electronegative metal, such as copper; and a surfactant in an amount of 50 ppm to 20,000 ppm based on the total weight of the cleaner-coater composition; and

[0222] An electrodepositable coating composition for at least partially coating the portion of the surface of the substrate treated with the cleaner-coater composition.

[0223] 14. The system of aspect 12 or aspect 13, wherein the electrodepositable coating composition comprises an electrodepositable binder comprising an active hydrogen containing, ionic salt group containing film forming polymer; a curing agent and a platy pigment.

[0224] 15. The system of aspect 14, wherein the electrodepositable coating composition comprises a platy pigment at a pigment to binder ratio of 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.

[0225] 16. The system of aspect 14 or aspect 15, wherein the platy pigment comprises an average equivalent spherical diameter of at least:

[0226] (a) at least 50 nm, such as at least 0.2 microns, such as at least 0.4 microns, such as at least 0.6 microns, such as at least 1 micron, such as at least 2 microns, such as at least 3 microns, such as at least 4 microns, such as at least 5 microns, as measured by dynamic light scattering;

[0227] (b) 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, as measured by dynamic light scattering; and / or

[0228] (c) 50 nm to 25 micrometers, such as 0.2 micrometers to 15 micrometers, such as 0.4 to 10 micrometers, such as 0.6 micrometers to 5 micrometers, such as 1 micrometer to 3.5 micrometers, such as 2 micrometers to 15 micrometers, such as 3 micrometers to 10 micrometers, such as 4 micrometers to 25 micrometers, such as 5 micrometers to 25 micrometers, such as 50 nm to 2.5 micrometers, such as 0.2 micrometers to 1.9 micrometers, such as 0.4 micrometers to 1.5 micrometers, such as 50 nm to 1 micrometer, as measured by dynamic light scattering.

[0229] 17. The system of any of aspects 14-16, wherein the platy pigment comprises a phyllosilicate pigment such as mica, chlorite, serpentine, talc, clay such as kaolin, or a combination thereof.

[0230] 18. The system of any of aspects 12-17, wherein the electrodepositable coating composition comprises a film-forming polymer comprising a blocked polyisocyanate, an aminoplast, a phenoplast, or a combination thereof.

[0231] 19. The system of any of aspects 12-18, wherein the system does not include a separate cleaning step.

[0232] 20. The system of any of aspects 12-19, further comprising a pre-spray composition comprising a surfactant in an amount of 50 ppm to 20,000 ppm based on the total weight of the pre-spray composition.

[0233] 21. The system of aspect 20, wherein the surfactant comprises a cationic surfactant, an anionic surfactant, a non-ionic surfactant, an amphoteric surfactant, or a combination thereof.

[0234] 22. The system of aspect 20 or aspect 21, wherein the pre-spray composition comprises the surfactant in an amount of:

[0235] (a) at least 50 ppm, such as at least 100 ppm, such as at least 200 ppm, such as at least 500 ppm, based on the total weight of the pre-spray composition;

[0236] (b) no more than 20,000 ppm, such as no more than 10,000 ppm, such as no more than 7,500 ppm, such as no more than 5,000 ppm, based on the total weight of the pre-spray composition; and / or

[0237] (c) from 50 ppm to 20,000 ppm, such as from 100 ppm to 10,000 ppm, such as from 200 ppm to 7,500 ppm, such as from 500 ppm to 5,000 ppm, based on the total weight of the pre-spray composition.

[0238] 23. The system according to any one of aspects 20 to 22, wherein the pre-spray composition further comprises a builder.

[0239] 24. The system according to aspect 23, wherein the builder comprises a phosphonate, such as a mono-, di- phosphonate, such as etidronic acid, and / or a poly-phosphonate, and / or wherein the builder comprises a sugar alcohol, such as sorbitol.

[0240] 25. The system according to aspect 23 or aspect 24, wherein the pre-spray composition comprises the builder in an amount of:

[0241] (a) at least 5 ppm, such as at least 10 ppm, such as at least 50 ppm, based on the total weight of the pre-spray composition;

[0242] (b) no more than 2,000 ppm, such as no more than 1,500 ppm, such as no more than 1,000 ppm, based on the total weight of the pre-spray composition; and / or

[0243] (c) from 5 ppm to 5,000 ppm, such as from 20 ppm to 2,000 ppm, such as from 50 ppm to 1,000 ppm, based on the total weight of the pre-spray composition.

[0244] 26. The system according to any one of aspects 20 to 22, wherein the pre-spray composition is substantially free, or essentially free, or completely free of a builder.

[0245] 27. The system according to any one of aspects 20 to 26, wherein the system does not comprise a rinsing step.

[0246] 28. A method of coating a substrate, comprising applying a composition according to any one of aspects 1 to 11 to a portion of a surface of the substrate.

[0247] 29. A method of coating a substrate, the method comprising:

[0248] applying a cleaner-coat composition according to any one of aspects 12 to 27 to a portion of a surface of the substrate; and

[0249] applying an electrodepositable coating composition according to any one of aspects 12 to 27 to at least a portion of the surface of the substrate to which the cleaner-coat composition was applied.

[0250] 30. The method according to aspect 29, wherein the method does not comprise a separate cleaning step.

[0251] 31. The method according to any one of aspects 28 to 30, further comprising applying a pre-spray composition according to any one of aspects 20 to 27 to the surface of the substrate.

[0252] 32. The method according to aspect 31, wherein the pre-spray composition is applied prior to the cleaner-coater composition.

[0253] 33. The method according to aspect 31 or aspect 32, wherein the method does not comprise a rinsing step.

[0254] 34. A substrate treated by the cleaner-coater composition according to any one of aspects 1 to 11.

[0255] 35. A substrate treated by the system according to any one of aspects 12 to 27.

[0256] 36. A substrate treated according to the method according to any one of aspects 28 to 33.

[0257] 37. The substrate according to any one of aspects 34 to 36, comprising a coating formed on at least a portion of a surface of the substrate by applying the cleaner-coater composition on the at least a portion of the surface of the substrate.

[0258] 38. The substrate according to aspect 37, wherein the coating comprises the Group IVB metal and / or the positively electronegative metal.

[0259] 39. The substrate according to any one of aspects 34 to 38, wherein the coating comprises:

[0260] (a) the Group IVB metal and the positively electronegative metal in a weight ratio of:

[0261] (i) at least 1 : 10, such as at least 3 : 22, such as at least 1 : 6;

[0262] (ii) not more than 2 : 1, such as not more than 1 : 1, such as not more than 1 : 2; and / or

[0263] (iii) 1 : 10 to 2 : 1, such as 3 : 22 to 1 : 1, such as 1 : 6 to 1 : 2;

[0264] (b) the Group IVB metal in an amount of less than 50 mg / m 2 as measured by ICP-OES; and / or

[0265] (c) the electropositive metal in an amount less than 5 mg / m 2 as measured by ICP-OES.

[0266] 40. The substrate of any one of aspects 34-39, further comprising a second coating formed on at least a portion of the coating formed from the cleaner-coater composition by applying the electrodepositable coating composition on the at least a portion of the coating formed from the cleaner-coater composition.

[0267] 41. The substrate of any one of aspects 34-40, wherein the substrate comprises an article, a part, or a combination thereof.

[0268] 42. The substrate of aspect 41, wherein the article comprises a vehicle, an appliance, a personal electronic device, a circuit board, a battery cell, a multi-metal substrate, or a combination thereof.

[0269] 43. The substrate of aspect 41, wherein the part comprises a vehicle part.

[0270] 44. The substrate of aspect 42, wherein the vehicle comprises a land vehicle or an aircraft.

[0271] 45. The substrate of any one of aspects 37-44, further comprising a second coating formed by applying an electrodepositable coating composition to at least a portion of the surface of the substrate comprising the first coating.

[0272] 46. Use of a coating formed from the cleaner-coater composition of any one of aspects 1-11 to provide a coating comprising:

[0273] (a) the Group IVB metal and the electropositive metal in a weight ratio of:

[0274] (i) at least 1 : 10, such as at least 3 : 22, such as at least 1 : 6;

[0275] (ii) no more than 2 : 1, such as no more than 1 : 1, such as no more than 1 : 2; and / or

[0276] (iii) 1 : 10 to 2 : 1, such as 3 : 22 to 1 : 1, such as 1 : 6 to 1 : 2;

[0277] (b) the Group IVB metal in an amount less than 50 mg / m 2 as measured by ICP-OES; and / or

[0278] (c) the electropositive metal in an amount less than 5 mg / m 2 as measured by ICP-OES.

[0279] 47. Use of a coating formed from the cleaner-coating agent composition according to any one of aspects 12 to 25 to provide a coating comprising:

[0280] (a) the Group IVB metal and the electropositive metal in a weight ratio of:

[0281] (i) at least 1 : 10, such as at least 3:22, such as at least 1 :6;

[0282] (ii) no more than 2: 1, such as no more than 1 : 1, such as no more than 1 :2; and / or

[0283] (iii) 1 : 10 to 2: 1, such as 3:22 to 1 : 1, such as 1 :6 to 1 :2;

[0284] (b) the Group IVB metal in an amount less than 50 mg / m 2 as measured by ICP-OES; and / or

[0285] (c) the electropositive metal in an amount less than 5 mg / m 2 as measured by ICP-OES.

[0286] 48. A substrate comprising a first coating on at least a portion of a surface of the substrate, the coating comprising:

[0287] (a) the Group IVB metal and the electropositive metal in a weight ratio of:

[0288] (i) at least 1 : 10, such as at least 3:22, such as at least 1 :6;

[0289] (ii) no more than 2: 1, such as no more than 1 : 1, such as no more than 1 :2; and / or

[0290] (iii) 1 : 10 to 2: 1, such as 3:22 to 1 : 1, such as 1 :6 to 1 :2;

[0291] (b) the Group IVB metal in an amount less than 50 mg / m 2 as measured by ICP-OES; and / or

[0292] (c) the electropositive metal in an amount less than 5 mg / m 2 as measured by ICP-OES.

[0293] While 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 could be developed in light of the overall teachings of the present disclosure. Accordingly, the particular arrangements disclosed are meant to be illustrative only and not limiting as to the scope of the present disclosure, which is defined by the appended claims and their full scope of equivalents, regardless.

[0294] Example

[0295] Preparing the composition

[0296] Detergents, pretreatments, and detergent-coating agent compositions are prepared using additives and surfactants as described in the present disclosure.

[0297] Preparation of alkaline cleaner:

[0298] An alkaline cleaner solution (C1) was prepared in a rectangular stainless steel tank equipped with a nozzle using Chemkleen Surface Prep 1R (CKSP1R), an alkaline cleaner, and Chemkleen 185A, a blended surfactant additive, both available from PPG Industries, Inc.

[0299] Preparation of pre-spray composition:

[0300] Pre-spray composition (P-S): A 37-gallon total volume rectangular stainless steel tank equipped with a nozzle was filled with 10 gallons of deionized water. To this was added Chemkleen 185A surfactant (38 mL), etidronic acid (2.88 g), 85% phosphoric acid (3 g), and sodium tripolyphosphate (25 g).

[0301] Preparation of pretreatment:

[0302] Pretreatment composition (PT1) was prepared by preparing Zircobond 1.5, available from PPG Industries, Inc., according to the manufacturer’s instructions.

[0303] Preparation of detergent-coating agent:

[0304] Cleaner-coat 1 (C-C1) Pre-spray composition (P-S): A 37-gallon total volume rectangular stainless steel tank equipped with a nozzle was filled with 10 gallons of deionized water. To this was added Chemkleen 185A surfactant (38 mL), etidronic acid (2.88 g), 85% phosphoric acid (3 g), and sodium tripolyphosphate (25 g).

[0305] Cleaner-coat 2 (C-C2) A 37-gallon total volume rectangular stainless steel tank equipped with a nozzle was filled with 10 gallons of deionized water. To this was added fluorozirconic acid (193.2 g), etidronate (9.6 g), 2% copper (II) nitrate solution (10 g), and Chemkleen 185A surfactant (38 mL).

[0306] C-C1 was circulated and maintained at 120 °F (50 °C) using an immersion heater (Polyscience Sous Vide Professional, Model #7306AC1B5, available from Polyscience, Niles, Illinois) and set to high agitation mode during the immersion panel to circulate and heat the composition contained therein.

[0307] After all ingredients were added to C-C1 and C-C2, free fluoride was measured using a DualStar pH / ISE dual channel benchtop meter (available from ThermoFisher Scientific) equipped with a fluoride selective electrode (Orion ISE Fluoride Electrode, Solid State, available from ThermoFisher Scientific) by immersing the ISE in the solution and allowing the measurement to come to equilibrium. Free fluoride was adjusted as needed with Chemfos AFL, a partially neutralized aqueous ammonium bifluoride solution, available from PPG Industries, Inc.

[0308] pH was measured using a pH meter (Interface, DualStar pH / ISE dual channel benchtop meter, available from ThermoFisher Scientific, Waitham, MA, USA) and a pH probe (Fisher Scientific ACCUMET pH Probe (Ag / AgCl Reference Electrode)) by immersing the pH probe in the solution. The pH of C-C1 and C-C2 was adjusted as needed to pH 4.5, while the pH of P-S was adjusted as needed to pH 7 with Chemfil Buffer, available from PPG Industries, Inc.

[0309] The amount of copper in each bath was measured using a DR / 890 colorimeter (available from HACH, Loveland, Colorado, USA) using an indicator (CuVer2 Copper Reagent Powder Pillows, available from HACH).

[0310] Table 1

[0311]

[0312] Preparation of a phosphate acryl polyol:

[0313] Component 1 listed in Table 2 below was added to a flask set up to full reflux under nitrogen with stirring and heated to 120 °C. Components 9 and 10 (initiator charge 1) were added dropwise to the flask over 3 hours 35 minutes. Five minutes after the start of initiator charge 1, components 2-8 (monomer charge) were mixed in an addition funnel and added dropwise over 3.5 hours. Once the monomer charge was complete, charge 13 was used to rinse the monomer charge addition funnel. After both charges were complete, the reaction was held at 120 °C for 1 hour. Then, components 11 and 12 (initiator charge 2) were added dropwise to the reaction flask via an addition funnel over 30 min. After the completion of initiator charge 2, component 14 was used to rinse the addition funnel. The reaction was held at 120 °C for 90 minutes and then allowed to cool to room temperature with stirring. The resulting phosphate acryl polyol resin had a solids content of 56 wt%.

[0314] Table 2

[0315]

[0316]

[0317] 1 Solvay Iboma

[0318] 2 Styrene from Millipore Sigma

[0319] 3 Acrylic acid-2-ethylhexyl ester from Dow

[0320] 4 Tert-dodecyl mercaptan from Arkema

[0321] 5 PAM-200 is a phosphoalkyl (meth)acrylate monomer from Solvay

[0322] 6 Acrylic acid-2-hydroxyethyl ester from BASF

[0323] 7 Hydroxy-functional methacrylate monomer from Dow

[0324] 8 Luperox 575 from Arkema

[0325] Preparation of Electrophoretic Paint A:

[0326] Electrophoretic paint A, a highly filled cationic amine functional epoxy / isocyanate crosslinked electrophoretic paint with platy pigments, was prepared. Components 1-4 listed in Table 3 below were mixed in a stainless steel beaker and mixed under high shear (2500 RPM using a 1.5 inch Cowles blade powered by a Fawcett pneumatic motor model 103A) for 5 minutes starting at 40°C. The temperature was raised above 60°C and the mixture was maintained under the above mixing for one hour after which the degree of dispersion was determined by a Hegman gage. When a minimum reading of 5 was achieved, the dispersion was determined to be well dispersed.

[0327] For the dispersion step, a mixture of components 5 and 6 were added to the mixture. A temperature below 60°C was established and the dispersion was mixed with 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 and mixed for one hour to bring the final solids of the dispersion paste to 40 wt.%. Component 8 was then added to the dispersed formulation and allowed to mix at ambient temperature for one hour to complete the high solids charge. To generate electrophoretic paint A, the high solids charge was further diluted to 25 wt.% solids with component 9.

[0328] Table 3

[0329]

[0330] 1 ASP200 clay, available from BASF

[0331] 2 See above for phosphorylated acrylic polyol

[0332] Preparation of Electrophoretic Paint B

[0333] Electrophoretic paint B, a commercially available cationic electrodepositable coating composition with 0.15 P:B, was prepared according to the manufacturer’s instructions.

[0334] Examples 1 to 4

[0335] The panels used for Examples 1-4 were prepared using cold rolled steel (CRS) and aluminum alloy 6111 (AA6111), both provided by ACT Test Panels (Hillsdale, MI).

[0336] The panels were treated using treatment methods A, B, C, or D listed in Tables 4, 5, 6, and 7, respectively.

[0337] For panels treated according to Treatment Method A, the panels were spray cleaned in cleaner (120°F) using Vee-jet nozzles at 10-15 psi for 120 seconds and rinsed with deionized water by immersion in a deionized water bath (75°F) for 30 seconds followed by a deionized water spray rinse using a Melnor back- trigger 7-type nozzle set to shower mode. The panels were then immersed in pretreatment for 120 seconds (80°F), rinsed with a deionized water spray rinse using a Melnor back- trigger 7-type nozzle set to shower mode (75°F) for 30 seconds, and dried with hot air (140°F) using a Hi-Velocity hand-held blower for 120 seconds.

[0338] For panels treated according to Treatment Method B, the panels were spray cleaned in cleaner (120°F) using Vee nozzles at 10-15 psi for 120 seconds and rinsed with a deionized water spray rinse using a Melnor back- trigger 7-type nozzle set to shower mode (75°F) for 30 seconds, and dried with hot air (140°F) using a high-speed hand-held blower manufactured by Dyson® (model 078302-300-000) at high setting for 120 seconds.

[0339] For panels treated according to Treatment Method C, the panels were immersion washed for 120 seconds (120°F), rinsed with a deionized water spray rinse using a Melnor back- trigger 7-type nozzle set to shower mode (75°F) for 30 seconds, and dried with hot air (140°F) using a high-speed hand-held blower for 120 seconds.

[0340] For panels treated according to Treatment Method D, the panels were spray washed in pre-spray (120°F) using Vee nozzles at 10-15 psi for 120 seconds. The panels were then immersed in additional cleaner for 120 seconds (120°F), rinsed with a deionized water spray rinse using a Melnor back- trigger 7-type nozzle set to shower mode (75°F) for 30 seconds, and dried with hot air (140°F) using a high-speed hand-held blower for 120 seconds.

[0341] Table 4. Treatment Method A

[0342] Step 1A Cleaner (120 seconds, 120°F, spray application) Step 2A Deionized water rinse (30 seconds, 75°F, immersion application) Step 3A Deionized water rinse (30 seconds, 75°F, spray application) Step 4A Pre-treatment (120-240 seconds, 80°F, immersion application) Step 5A Deionized water rinse (30 seconds, 75°F, spray application) Step 6A Hot air drying (120 seconds, 140°F)

[0343] Table 5. Treatment Method B

[0344] Step 1B Cleaner (120 seconds, 120°F, spray application) Step 2B Deionized water rinse (30 seconds, 75°F, spray application) Step 3B Hot air drying (120 seconds, 140°F)

[0345] Table 6. Treatment Method C

[0346] Step 1C Cleaner (120 seconds, 120°F, immersion application) Step 2C Deionized water rinse (30 seconds, 75°F, spray application) Step 3C Hot air drying (120 seconds, 140°F)

[0347] Table 7. Treatment Method D

[0348] Step 1D Pre-spray (60 seconds, 120°F, spray application) Step 2D Cleaner (120 seconds, 120°F, immersion application) Step 3D Deionized water rinse (30 seconds, 75°F, spray application) Step 4D Hot air drying (120 seconds, 140°F)

[0349] After completion of the treatment method A, B, C, or D, the panels were coated with either Electrophoretic Paint A or Electrophoretic Paint B (a cationic electrophoretic paint with 0.15 P:B).

[0350] Each test panel was immersed in the electrophoretic paint and electrodeposited using a DC power supply powered rectifier (Xantrax Model XFR600-2, Elkhart, Indiana; or Sorensen XZG 300-5.6, Ametek, Berwyn, Pennsylvania). The exact coating conditions and film thickness for each paint are listed in Table 8. After electrophoretic painting of the panels, each panel was rinsed with deionized water and baked in an electric oven (Despatch Model LFD-1-42) at 177 °C.

[0351] Table 8

[0352]

[0353]

[0354] The electrophoretically painted panels were scribed vertically down one side of the panel to the metal substrate. To perform the corrosion performance evaluation, the panels were placed in CASS (Copper Accelerated Aceto Acetate Salt Spray) testing for a minimum of 20 days or in GMW14872 testing for a minimum of 30 cycles (i.e., 30 days). At the end of the testing, the panels were rated by measuring the paint loss from the scribe (creep) and the maximum creep (both sides) of each panel in millimeters. After exposure, the corroded panels were dried under ambient conditions. The loose coating around the scribe was removed by applying a Scotch® brand filament tape (3M Industries Adhesives and Tapes Divisions, St. Paul, MN) and pulling it off. The width of the exposed metal area along the scribe was then recorded for 5 to 12 locations and averaged to evaluate the corrosion performance of the panel. As used herein, scribe creep refers to the area of paint loss around the scribe caused by corrosion or delamination (e.g., affected paint to affected paint). Panel replicates were run for each condition and the results were averaged.

[0355] Zirconium deposition of non-electrophoretically coated panels was analyzed using handheld X-ray fluorescence (XRF) measured with Oxford Instruments' X-Met 8000 as described below; operating parameters for Zirconium and Copper: 120 second timed measurement, 40Kv, 9pA, K alpha, T(p) = 1.1pS (reported as XRF peak area Zr net counts). Peak area was calculated by adding the XRF counts or peak of the respective element in the region of interest (ROI) and then subtracting the counts from an untreated control panel.

[0356] Example 1

[0357] CRS and AA6111 panels were treated with different treatment baths and treatment methods. The panels were then electrophoretically coated with electrophoretic paint B according to the parameters described above. The panels were scribed and subjected to corrosion testing as specified in Table 9.

[0358] Table 9

[0359]

[0360] Example 1 demonstrates that CRS and AA6111 substrates treated with C-C1 have improved or comparable corrosion performance to substrates treated with C1 + PT1 and significantly improved corrosion performance to substrates treated with C1 alone. Furthermore, C-C1 treatment using treatment method C has good corrosion performance with fewer process steps than C1 + PT1 treatment using treatment method A.

[0361] Example 2

[0362] CRS and AA6111 panels were treated with different treatment baths and treatment methods. The panels were then electrophoretically coated with electrophoretic paint A according to the parameters described above. The panels were scribed and subjected to corrosion testing as specified in Table 10.

[0363] Table 10

[0364]

[0365] Example 2 demonstrates that substrates treated with C-C2 exhibit good corrosion performance on CRS and AA6111 compared to substrates treated with C1 + PT1 and better corrosion performance on CRS and AA6111 than substrates treated with C1 and electrophoretic paint A. Overall, substrates treated with C-C2 demonstrate good corrosion performance with fewer process steps than substrates treated with P-S + C-C1 and both substrates treated with C-C2 and P-S + C-C1 have even fewer process steps than substrates treated with C1 + PT1.

[0366] Example 3

[0367] CRS and AA6111 panels were treated with different treatment baths and treatment methods and coated with different electrophoretic paints. The panels were scribed and subjected to corrosion testing as specified in Table 11.

[0368] Table 11

[0369]

[0370] Example 3 demonstrates that substrates treated with C-C2 and electrophoretic paint A have improved corrosion performance on CRS and AA6111 compared to substrates treated with CI + PT1 and electrophoretic paint B. Substrates treated with C-C2 and electrophoretic paint A have much better corrosion performance on CRS and AA6111 than substrates treated with CI and electrophoretic paint A or electrophoretic paint B. Thus, treating substrates with C-C2 achieves good corrosion performance with fewer process steps than treating substrates with CI + PT1.

[0371] Example 4

[0372] CRS panels were treated with different treatment baths and treatment methods and exposed to 25 mL of 6N hydrochloric acid for 5 minutes to dissolve the pre-treatment layer. Each etchant solution was submitted for ICP-OES and the concentration of Cu and Zr was measured. These were converted to coating weights (milligrams per square meter) for each condition. In addition, CRS panels treated with different treatment baths and treatment methods were analyzed using a handheld XRF using the same parameters described above. The results are summarized in Table 12.

[0373] Table 12

[0374]

[0375] Example 4 demonstrates that C-C1 and C-C2 treatments result in much lower Zr ICP coating weights and Zr XRF deposition compared to the comparative treatment CI + PT1. All three treatments result in comparable Cu ICP coating weights but slightly higher Cu XRF deposition. Substrates treated with C-C1 and C-C2 exhibit lower Zr ICP coating weights and Zr XRF deposition compared to substrates treated with CI + PT1 while showing improved or comparable corrosion performance as shown in Examples 1-3 above. Thus, substrates treated with the cleaner-coating agent compositions of the present disclosure provide comparable or improved corrosion performance with fewer steps and lower Zr deposition compared to substrates treated with cleaning and pre-treatment compositions.

Claims

1. A cleaner-coat composition comprising: a Group IVB metal in an amount of 50 ppm to 8,000 ppm based on the total weight of the cleaner-coat composition; a positively charged metal; a builder comprising a phosphonate and / or a sugar alcohol; and a cleaner-coat surfactant in an amount of 50 ppm to 20,000 ppm based on the total weight of the cleaner-coat composition.

2. The cleaner-coat composition of claim 1, wherein the Group IVB metal comprises zirconium, titanium, or a combination thereof, wherein the Group IVB metal is optionally provided by hexafluorozirconic acid, hexafluorotitanic acid, a salt thereof, or a combination thereof.

3. The cleaner-coat composition of claim 1 or claim 2, wherein the cleaner-coat composition comprises: (a) the positively charged metal in an amount of 2 ppm to 200 ppm based on the total weight of the cleaner-coat composition; and / or (b) the cleaner-coat surfactant in an amount of 100 ppm to 10,000 ppm based on the total weight of the cleaner-coat composition; and / or (c) the builder in an amount of 10 ppm to 2,500 ppm based on the total weight of the cleaner-coat composition.

4. The cleaner-coat composition of any one of the preceding claims, wherein the positively charged metal comprises copper.

5. The cleaner-coat composition of any one of the preceding claims, wherein the phosphonate comprises a mono-phosphonate, a di-phosphonate such as etidronic acid, and / or a poly-phosphonate, and / or the sugar alcohol comprises sorbitol.

6. The cleaner-coat composition of any one of the preceding claims, wherein the cleaner-coat composition comprises a pH of 1.0 to 6.

0.

7. The cleaner-coat composition of any one of the preceding claims, wherein the cleaner-coat composition is substantially free of phosphate and / or sodium nitrobenzenesulfonate.

8. The cleaner-coat composition of any one of the preceding claims, wherein the cleaner-coat composition further comprises: (d) total fluoride, optionally in an amount of 60 ppm to 10,000 ppm based on the total weight of the cleaner-coat composition; and / or (e) free fluoride, optionally in an amount of 25 ppm to 750 ppm based on the total weight of the cleaner-coat composition.

9. A system for treating a substrate, the system comprising: (a) the cleaner-coat composition of any one of the preceding claims for treating at least a portion of a surface of the substrate; and (b) an electrodepositable coating composition for at least partially coating the portion of the surface of the substrate treated with the cleaner-coat composition.

10. The system of claim 9, wherein the electrodepositable coating composition comprises an ionically salt group-containing film-forming polymer and / or a curing agent, such as a blocked polyisocyanate, an aminoplast resin, a phenolic plastic resin, or a combination thereof.

11. The system of claim 9 or claim 10, wherein the electrodepositable coating composition comprises a platy pigment, the platy pigment being present at a ratio of pigment to binder of at least 0.4:

1.

12. A system for treating a substrate, the system comprising: a cleaner-coat composition comprising: a Group IVB metal in an amount of 50 ppm to 8,000 ppm based on the total weight of the cleaner-coat composition; a positively electronegative metal, such as copper; and a surfactant in an amount of 50 ppm to 20,000 ppm based on the total weight of the cleaner-coat composition, for treating at least a portion of a surface of the substrate; and 14. The system of any one of claims 9 to 13, further comprising: an electrodepositable coating composition for at least partially coating the portion of the surface of the substrate treated with the cleaner-coat composition, wherein the electrodepositable coating composition comprises: an electrodepositable binder comprising an active hydrogen-containing, ionically salt group-containing film-forming polymer; a curing agent; and a platy pigment, wherein the platy pigment is present at a ratio of pigment to binder of at least 0.4:

1.

13. The system of claim 11 or claim 12, wherein the platy pigment has an average equivalent spherical diameter of 50 nm to 25 microns. a pre-spray composition comprising a builder and a surfactant, the pre-spray composition being in an amount of 50 ppm to 20,000 ppm based on the total weight of the pre-spray composition.

15. A method for coating a substrate, the method comprising applying the cleaner-coat composition of any one of claims 1 to 8 to at least a portion of a surface of the substrate.

16. A method of treating a substrate, the method comprising: applying the cleaner-coat composition of any one of claims 9 to 14 to at least a portion of a surface of the substrate; and applying the electrodepositable coating composition of claims 9 to 14 to at least a portion of the surface of the substrate to which the cleaner-coat composition was applied.

17. The method of claim 16, wherein the method does not include a separate rinsing step.

18. The method of claim 16 or claim 17, further comprising applying the pre-spray composition of claim 14.

19. The method of claim 18, wherein the method does not include a rinsing step.

20. A substrate treated by the system of any one of claims 9 to 14.

21. A substrate according to the method of any one of claims 15 to 19.

22. The substrate according to claim 20 or claim 21, comprising a coating formed on at least a portion of a surface of the substrate by applying the cleaner-coating agent composition on the at least a portion of the surface of the substrate.

23. The substrate according to claim 22, wherein the coating comprises: (a) the Group IVB metal and the positively electronegative metal in a weight ratio of: (i) at least 1 : 10, such as at least 3 : 22, such as at least 1 : 6; (ii) no more than 2 : 1, such as no more than 1 : 1, such as no more than 1 : 2; and / or (iii) 1 : 10 to 2 : 1, such as 3 : 22 to 1 : 1, such as 1 : 6 to 1 : 2; 24. The substrate according to claim 23, wherein the coating comprises: (a) the Group IVB metal and the positively electronegative metal in a weight ratio of: (i) at least 1 : 10, such as at least 3 : 22, such as at least 1 : 6; (ii) no more than 2 : 1, such as no more than 1 : 1, such as no more than 1 : 2; and / or (iii) 1 : 10 to 2 : 1, such as 3 : 22 to 1 : 1, such as 1 : 6 to 1 :

2. (b) the Group IVB metal in an amount less than 50 mg / m 2 as measured by ICP-OES; and / or (c) the electropositive metal in an amount of at least 5 mg / m 2 as measured by ICP-OES.

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