Compositions, systems, and methods for processing substrates

Abstract

This disclosure is directed to a cleaner coater composition comprising a builder 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, an electropositive metal, a phosphonic acid and / or 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. This disclosure is also directed to a system and method for processing a substrate comprising any of the cleaner coater compositions and electrodepositable coating compositions disclosed herein. This disclosure is also directed to a substrate processed by any of the cleaner coater compositions, systems, and / or methods disclosed herein.

Description

[Technical Field]

[0001] This disclosure relates to compositions, systems, and methods for processing substrates. [Background technology]

[0002] It is common practice to improve corrosion resistance and paint adhesion by applying a protective coating to a metal substrate. Typically, the surface of the substrate is treated by sequentially applying (1) a cleaning composition, (2) a pretreatment composition, and (3) an electrodepositable coating composition. [Overview of the project]

[0003] This specification discloses a cleaner coater composition comprising a builder containing a group IVB metal, an electropositive metal, a phosphonate and / or sugar alcohol in an amount of 50 ppm to 8,000 ppm based on the total weight of the cleaner coater composition, 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.

[0004] The disclosure is further directed to a system for processing a substrate, comprising (a) any of the cleaner coater compositions disclosed herein for processing at least a portion of the surface of the substrate, and (b) any of the electrodepositable coating compositions disclosed herein for at least partially coating the portion of the surface of the substrate processed with the cleaner coater composition.

[0005] The disclosure is further directed to a system for processing a substrate, comprising a cleaner coater composition comprising a cleaner coater composition comprising 50 ppm to 8,000 ppm of a group IVB metal, an electropositive metal such as copper, and a surfactant comprising 50 ppm to 20,000 ppm of a surfactant comprising the total weight of the cleaner coater composition for processing at least a portion of the surface of the substrate, and an electrodepositable coating composition for at least partially coating a portion of the surface of the substrate processed with the cleaner coater composition.

[0006] This disclosure is further directed to a method for coating a substrate, which includes applying one of the cleaner coater compositions disclosed herein to at least a portion of the surface of the substrate.

[0007] This disclosure is further directed to a method for treating a substrate, comprising applying one of the cleaner coater compositions disclosed herein to at least a portion of the surface of the substrate, and applying one of the electrodepositable coating compositions disclosed herein to at least a portion of the surface of the substrate to which the cleaner coater composition has been applied.

[0008] This disclosure is further directed toward substrates processed in any of the systems disclosed herein.

[0009] This disclosure is further directed to substrates processed by any of the methods disclosed herein. [Modes for carrying out the invention]

[0010] For the purposes of the following detailed description, it should be understood that various alternative variations and sequences of steps may be assumed, unless expressly designated to be contrary. Furthermore, except in any example of operation, or unless otherwise indicated, all numbers, such as those representing values, quantities, percentages, ranges, subranges, and fractions, can be read as if preceded by the word “approximately,” even if the term does not explicitly appear. Thus, unless shown to be contrary, the numerical parameters described in the following specification and the appended claims are approximations that may vary depending on the desired characteristics obtained by the invention. At a minimum, and without intending to limit the application of the doctrine of equivalents to the claims, each numerical parameter should be interpreted by taking at least the reported significant figures into consideration and by applying the usual rounding technique. Where a closed or open-ended numerical range is described herein, all numbers, values, quantities, percentages, subranges, and fractions within or encompassed within the numerical range should be deemed to be specifically included in and belonging to the original disclosure of this application, as if those numbers, values, quantities, percentages, subranges, and fractions were explicitly written out in their entirety.

[0011] While the numerical ranges and parameters representing the broad scope of this disclosure are approximations, the numerical values ​​shown in the specific examples are reported as accurately as possible. However, any numerical value inherently contains a certain degree of error, which is necessarily derived from the standard deviation observed in the respective test measurements of those values.

[0012] Where used herein, unless otherwise specified, plural terms may encompass their singular counterparts, and vice versa. For example, where herein we refer to “a group IVB metals” and “an electropositive metals,” combinations (i.e., plurals) of these components may be used.

[0013] In addition, in this application, even if "and / or" may be explicitly used in certain cases, unless otherwise specified, the use of "or" means "and / or".

[0014] As used herein, “including,” “containing,” and similar terms are understood to be synonymous with “comprising” in the context of this application, and are therefore open-ended and do not exclude the presence of additional undescribed or undisclosed elements, materials, components, or method steps. As used herein, “consisting of” is understood to exclude the presence of any unspecified elements, components, or method steps in the context of this application. As used herein, “consisting essentially of” is understood to include specific elements, materials, components, or method steps, and those described that do not significantly affect the “basic and novel features.” Open-ended terms include closed terms, for example, “comprising” includes “consisting of” and “consisting essentially of.”

[0015] As used herein, the terms “on,” “onto,” “applied on,” “applied onto,” “formed on,” “deposited on,” and “deposited onto” mean that something is formed on, layered on, deposited on, or provided on a surface, but not necessarily in contact with the surface. For example, a composition “applied on” a substrate does not preclude the presence of one or more other interposing coating layers of the same or different compositions located between the composition and the substrate.

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

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

[0018] As used herein, "cleaner - coater composition" is a composition prepared for cleaning and / or degreasing the surface of a substrate, and refers to a composition that functions as a pretreatment composition while removing fats, dirt, oils, and / or other foreign substances.

[0019] As used herein, "pretreatment composition" refers to a composition that can react with a substrate surface, chemically change the substrate surface, and form a coating that binds thereto to provide corrosion protection. The pretreatment composition can be an aqueous composition.

[0020] As used herein, "Group IVB metal" refers to an element belonging to Group IVB of the CAS version of the periodic table of elements as shown in, for example, the Handbook of Chemistry and Physics, 63rd Edition (1983), and corresponds to Group 4 in the actual IUPAC numbering.

[0021] As used herein, "Group IVB metal compound" refers to a compound containing an element belonging to Group IVB of the CAS version of the periodic table of elements.

[0022] As used herein, "surfactant" refers to a molecule that suspends, entraps, or emulsifies organic - containing contaminants. A surfactant contains a hydrophilic portion and a hydrophobic portion and reduces the surface tension between two liquids, a liquid and a gas, or a liquid and a solid.

[0023] As used herein, “builder” refers to a compound capable of removing metals from a composition through chelating, ionic interaction, or precipitation. Builders do not have emulsifying properties.

[0024] As used herein, “coating composition” refers to a composition, such as a solution, mixture, or dispersion, that can form 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 a reactive material that may be added to cure a composition. As used herein, “cured,” “cured,” or similar terms mean that the reactive functional groups of the components forming the composition react to form a coating or bond.

[0026] As used herein, “salt” refers to an ionic compound composed of a metallic or nonmetallic cation and a nonmetallic anion, with an overall electrical load of zero. Salts may be hydrated or anhydrous.

[0027] As used herein, “aqueous composition” or “aqueous coating composition” refers to a solution or dispersion in a medium primarily containing water. For example, an aqueous composition may contain more than 50% by weight, or more than 70% by weight, or more than 80% by weight, or more than 90% by weight, or more than 95% by weight of water based on the total weight of the composition. In other words, an aqueous composition may consist substantially of water, for example.

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

[0029] As used herein, "insoluble" means not dissolved in an aqueous medium.

[0030] As used herein, "soluble" means dissolved in an aqueous medium.

[0031] Ambient conditions generally refer to room temperature (23°C) and humidity conditions, or temperature and humidity conditions commonly found where the composition is applied to the substrate, e.g., 10°C to 32°C and relative humidity 4% to 80%, while slightly hot conditions mean temperatures slightly above ambient temperature. As used herein, “slightly hot conditions” refers to temperatures in the range of 32°C to 40°C.

[0032] As used herein, unless otherwise specified, the term “substantially absent” means that a particular material is present in a mixture or composition (or a coating formed therefrom) in an amount less than 5 parts per million (ppm) of the total weight of the mixture or composition (or a coating formed therefrom). As used herein, unless otherwise specified, the term “essentially absent” means that a particular material is present in a mixture or composition (or a coating formed therefrom) in an amount less than 1 ppm of the total weight of the mixture or composition (or a coating formed therefrom). As used herein, unless otherwise specified, the term “completely absent” means that a particular material is present in a mixture or composition (or a coating formed therefrom) in an amount less than 1 billion (ppb) of the total weight of the mixture or composition (or a coating formed therefrom), or that such material is below the detection limit of common analytical techniques. If a particular material is substantially absent, essentially absent, or completely absent in a mixture or composition (or a coating formed therefrom), this means that the material, in any form, is excluded from the mixture or composition (or a coating formed therefrom), except in cases where the material may be unintentionally present as a result of carryover from a previous treatment bath in the treatment line, contamination from a substrate, or the like.

[0033] Unless otherwise disclosed herein, as used herein, “total composition weight,” “total composition weight,” or similar terms refer to the total weight of all components present in each composition, including carriers and solvents.

[0034] As described above, this disclosure relates to a cleaner coater composition comprising a builder containing a group IVB metal, an electropositive metal, a phosphonate and / or sugar alcohol in an amount of 50 ppm to 8,000 ppm based on the total weight of the cleaner coater composition, 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 described above, this disclosure relates to a cleaner coater composition comprising a builder containing a group IVB metal, an electropositive metal, a phosphonate and / or sugar alcohol in an amount of 50 ppm to 8,000 ppm based on the total weight of the cleaner coater composition, 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 disclosure is also directed to a system for processing a substrate, comprising any of the cleaner coater compositions disclosed herein for processing at least a portion of the surface of the substrate, and any of the electrodepositable coating compositions disclosed herein for at least partially coating the portion of the surface of the substrate processed with the cleaner coater composition.

[0037] The disclosure is also directed to a system for processing a substrate, comprising: a cleaner coater composition comprising a cleaner coater composition comprising 50 ppm to 8,000 ppm of a group IVB metal, an electropositive metal such as copper, and a surfactant comprising 50 ppm to 20,000 ppm of a surfactant, based on the total weight of the cleaner coater composition, for processing at least a portion of the surface of the substrate; and an electrodepositable coating composition comprising an electrodepositable binder comprising an active hydrogen-containing ionic base-containing film-forming polymer, a curing agent, and a plate-like pigment present in a pigment-to-binder ratio of at least 0.4:1.

[0038] This disclosure is also directed to a method for coating a substrate, which includes applying one of the cleaner coater compositions disclosed herein.

[0039] The disclosure is also directed to a method for treating a substrate, comprising: applying one of the cleaner coater compositions disclosed herein to at least a portion of the surface of the substrate; and applying one of the electrodepositable coating compositions disclosed herein to at least a portion of the surface of the substrate to which the cleaner coater composition has been applied.

[0040] This disclosure is also directed to substrates processed in any of the systems disclosed herein.

[0041] This disclosure is also directed to substrates processed by any of the methods disclosed herein.

[0042] Cleaner coater composition The cleaner coater composition may essentially consist of, or may consist of, a group IVB metal, an electropositive metal, a surfactant, and optionally a builder and / or water.

[0043] The cleaner coater composition may contain Group IVB metals. Group IVB metals may include zirconium, titanium, hafnium, or combinations thereof. Group IVB metals may be provided in the form of acids or salts. For example, Group IVB metals may be compounds of zirconium, titanium, hafnium, or mixtures thereof. Suitable zirconium compounds include, but are not limited to, zirconic hexafluoride, alkali metals and their ammonium salts, zirconium tetrafluoride, ammonium zirconium carbonate, zirconium carboxylates and zirconium hydroxyl carboxylates, such as zirconium acetate, zirconium oxalate, ammonium zirconium glycolate, ammonium zirconium lactate, ammonium zirconium citrate, basic zirconium carbonate, zirconyl nitrate, zirconyl sulfate, oxides or hydroxides of zirconium, and mixtures thereof. Suitable titanium compounds include, but are not limited to, titanic hexafluoride, titanic fluoride, and salts thereof. Suitable hafnium compounds include, but are not limited to, hafnium nitrate.

[0044] Group IVB metals may be present in the cleaner coater composition in an amount of at least 50 ppm, for example, at least 100 ppm, for example, at least 150 ppm, for example, at least 200 ppm, for example, at least 500 ppm, for example, at least 600 ppm, for example, at least 700 ppm, for example, at least 800 ppm, for example, at least 900 ppm, based on the total weight of the cleaner coater composition. Group IVB metals may be present in the cleaner coater composition in an amount of 8,000 ppm or less, for example, 6,000 ppm or less, for example, 5,000 ppm or less, for example, 4,000 ppm or less, for example, 3,000 ppm or less, for example, 2,000 ppm or less, for example, 1,500 ppm or less, based on the total weight of the cleaner coater composition. Group IVB metals may be present in the cleaner coater composition in amounts ranging from 50 ppm to 8,000 ppm, for example, 100 ppm to 6,000 ppm, for example, 150 ppm to 4,000 ppm, for example, 200 ppm to 2,000 ppm, for example, 500 ppm to 5,000 ppm, for example, 500 ppm to 1,500 ppm, for example, 600 ppm to 4,000 ppm, for example, 700 ppm to 3,000 ppm, for example, 800 ppm to 2,000 ppm, and for example, 900 ppm to 1,500 ppm, based on the total weight of the clean coater composition.

[0045] Cleaner coater compositions may also contain electropositive metals. As used herein, “electropositive metal” refers to a metal that is more electrically electropositive than the metal substrate. This means that, for the purposes of this disclosure, the term “electropositive metal” encompasses metals that are less susceptible to oxidation than the metal of the metal substrate being treated. As will be understood by those skilled in the art, the tendency of a metal to oxidize is called its oxidation potential, expressed in volts, and measured relative to a standard hydrogen electrode, which is optionally assigned an oxidation potential of zero. The oxidation potentials of some elements are shown in Table 1 below. The voltage values ​​E in the table below for some elements * However, if the value is greater than that of the element being compared, that element is less susceptible to oxidation than the element being compared. [Table 1]

[0046] Metal substrates that may be used in this disclosure include, but are not limited to, cold-rolled steel, hot-rolled steel, zinc-coated steel, zinc compounds, or zinc alloys, hot-dip galvanized steel, galvanized steel, zinc-plated steel, aluminum alloys, aluminum-plated steel, aluminum alloy-plated steel, magnesium, and magnesium alloys. Suitable electropositive metals for deposition thereon include, for example, nickel, copper, silver, and gold, or mixtures thereof.

[0047] When the electropositive metal includes copper, both soluble and insoluble compounds can function as sources of copper in the cleaner coater composition. For example, a source of copper in the cleaner coater composition may be a water-soluble copper compound. Specific examples of such compounds include, but are not limited to, copper sulfate, copper nitrate, copper thiocyanate, disodium ethylenediaminetetraacetate tetrahydrate, copper bromide, copper oxide, copper hydroxide, copper chloride, copper fluoride, copper gluconate, copper citrate, copper lauroyl sarcosinate, 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, sodium copper chlorophyllin, copper silicofluoride, copper borofluoride, and copper iodate, as well as copper salts of carboxylic acids in the formic to decanoic acid congener series and copper salts of polybasic acids in the oxalic acid to suberic acid series.

[0048] When copper supplied from such water-soluble copper compounds precipitates as an impurity in the form of copper sulfate or copper oxide, it may be desirable to add a complexing agent that suppresses copper precipitation and therefore stabilizes the copper complex within the compound.

[0049] Copper compounds can be added as copper complex salts such as K3Cu(CN)4 or Cu-EDTA, which can exist self-stable in the cleaner coater composition, i.e., they do not precipitate. However, by combining the complexing agent with compounds that are difficult to self-dissolve, it is also possible to form copper complexes that can exist stably in the cleaner coater composition. Examples include copper cyanide complexes formed by combinations of CuCN and KCN, or CuSCN and KSCN or KCN, and Cu-EDTA complexes formed by combinations of CuSO4 and EDTA·2Na.

[0050] Electropositive metals may be present in the cleaner coater composition in an amount of at least 2 ppm, e.g., at least 10 ppm, e.g., at least 20 ppm, based on the total weight of the cleaner coater composition. Electropositive metals may be present in the cleaner coater composition in an amount of 200 ppm or less, e.g., 100 ppm or less, e.g., 75 ppm or less, e.g., 40 ppm or less, based on the total weight of the cleaner coater composition. Electropositive metals may be present in the cleaner coater composition in an amount of 2 ppm to 200 ppm, e.g., 2 ppm to 75 ppm, e.g., 10 ppm to 100 ppm, e.g., 20 ppm to 75 ppm, e.g., 20 ppm to 40 ppm, based on the total weight of the cleaner coater composition.

[0051] Cleaner coater compositions may contain surfactants. Surfactants may include cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, or combinations thereof. Suitable cationic surfactants include, but are not limited to, quaternary 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 sulfonates (such as Dowfax 2A1 available from The Dow Chemical Company), sulfates (such as Niaproof08 available from Niacet), phosphate esters (such as Triton H-66 available from The Dow Chemical Company), and ethers (such as Triton DF20 available from The Dow Chemical Company). Suitable nonionic surfactants include, but are not limited to, alcohol ethoxylates (e.g., Tomadol-1-n or Tomadol 91-6 available from Evonik Industries, SEACO 9AE available from Sea-Land Chemical Company, Makon NF-12 available from Surfachem, etc.) and alkylphenol ethoxylates (e.g., Triton X100 available from The Dow Chemical Company, etc.). Suitable amphoteric surfactants include, but are not limited to, alkylsultaines (e.g., Mirataine ASC and Mirataine CBS available from Solvay, etc.).

[0052] Surfactants may be present in the cleaner coater composition in an amount of at least 50 ppm, for example, at least 100 ppm, for example, at least 200 ppm, for example, at least 500 ppm, based on the total weight of the cleaner coater composition. Surfactants may be present in the cleaner coater composition in an amount of 20,000 ppm or less, for example, 10,000 ppm or less, for example, 7,500 ppm or less, for example, 5,000 ppm or less, based on the total weight of the cleaner coater composition. Surfactants may be present in the cleaner coater composition in an amount of 50 ppm to 20,000 ppm, for example, 100 ppm to 10,000 ppm, for example, 200 ppm to 7,500 ppm, for example, 500 ppm to 5,000 ppm, based on the total weight of the cleaner coater composition.

[0053] The cleaner coater composition may include a builder. The builder is essentially composed of, or may consist of, phosphonates such as sodium tripolyphosphate, carbonates, silicates, polycarboxylates, polyacrylates, gluconic acid, sugar alcohols, aminocarboxylates, or combinations thereof. Preferred phosphonates may include monophosphonates, diphosphonates, polyphosphonates, or combinations thereof.

[0054] Phosphonates may include phosphonic acids. Phosphonic acids may include monophosphonic acids, diphosphonic acids, polyphosphonic acids, or combinations thereof. For example, diphosphonic acids may include etidronic acid or its derivatives. Other suitable phosphonic acids may include ethylenediaminetetra(methylenephosphonic acid) (EDTMP), diethylenetriaminepenta(methylenephosphonic acid) (DTPMPA), iminodi(methylphosphonic acid), N-(phosphonomethyl)iminodiacetic acid hydrate, (aminomethyl)phosphonic acid, glyphosate, methylenediphosphonic acid, N,N-bis(phosphonomethyl)glycine, glyphosine, 2-phosphonobutane 1,2,4-tricarboxylic acid (PBTC), aminotris(methylenephosphonic acid) (ATMPaminotris), polyvinylphosphonic acid (PVPA), or combinations thereof.

[0055] The molecular weight (Mw) of the phosphonate may be at least 90 g / mol, for example, at least 100 g / mol, for example, at least 150 g / mol, for example, at least 200 g / mol. The Mw of the phosphonate may be 50,000 g / mol or less, for example, 40,000 g / mol or less, for example, 30,000 g / mol or less, for example, 1,000 g / mol or less, for example, 600 g / mol or less. The Mw of the phosphonate may be in the range of 90 g / mol to 50,000 g / mol, for example, 100 g / mol to 40,000 g / mol, for example, 150 g / mol to 30,000 g / mol, for example, 150 g / mol to 600 g / mol, for example, 200 g / mol to 1,000 g / mol, for example, in the range of 200 g / mol to 600 g / mol. As used herein, "Mw" refers to weight-average molecular weight, measured using a polystyrene standard and tetrahydrofuran (THF) as the solvent, at a flow rate of 1 ml min. -1 Therefore, the separation uses two PL Gel Mixed C columns, and the theoretical value is determined by gel permeation chromatography using a Waters2695 separation module and a Waters410 differential refractometer (RI detector).

[0056] The builder may be present in the cleaner coater composition in an amount of at least 10 ppm, for example, at least 30 ppm, for example, at least 50 ppm, based on the total weight of the cleaner coater composition. The builder may be present in the cleaner coater composition in an amount of 2,500 ppm or less, for example, 2,000 ppm or less, for example, 1,500 ppm or less, based on the total weight of the cleaner coater composition. The builder may be present in the cleaner coater composition in an amount of 10 ppm to 2,500 ppm, for example, 30 ppm to 2,000 ppm, for example, 50 ppm to 1,500 ppm, based on the total weight of the cleaner coater composition.

[0057] Cleaner coater compositions may optionally contain fluorides. Fluorides may be measured as total fluorides, including both free and bound fluorides. As used herein, “free fluorides” means fluorides present in the cleaner coater composition that are not bound to metal or hydrogen ions. As used herein, “bound fluorides” means fluorides containing fluoride anions in solution that are ionic or covalently bonded to metal cations or hydrogen ions. Such complexed fluoride ions cannot be measured with a fluoride ion selective electrode (ISE), however, if the solution containing the fluoride ions is mixed with an ionic strength adjustment buffer (e.g., citrate anion or EDTA) from which the fluoride ions are released from such complexes, the fluoride ions become measurable with a fluoride ISE at this point, and this measurement is known as “total fluorides.” Alternatively, the total fluoride can be calculated by comparing the weight of fluoride supplied to the cleaner coater composition with the total weight of the cleaner coater composition.

[0058] For example, free fluoride can be measured as an operating parameter in a cleaner coater composition bath using, for example, a fluoride ion-selective electrode ("ISE") available from Thermoscientific, a symphony® Fluoride Ion Selective Combination Electrode supplied by VWR International, or an Orion Dual Star Dual Channel Benchtop Meter equipped with a similar electrode. See, for example, Light and Cappuccino, Determination of fluoride in toothpaste using an ion-selective electrode, J. Chem. Educ., 52:4, 247-250, April 1975. Fluoride ISEs can be standardized by immersing the electrode in a solution of known fluoride concentration, recording readings in millivolts, and then plotting these millivolt readings on a logarithmic graph. Millivolt readings of unknown samples are then compared to this calibration graph to determine the fluoride concentration. Alternatively, a fluoride ISE can be used with a meter that performs calibration calculations internally, allowing for direct reading of the concentration of an unknown sample after calibration.

[0059] Free fluorides in the cleaner coater composition may originate from Group IVB metal sources present in the composition, such as hexazirconate hexafluoride or titanate hexafluoride. Furthermore, other polyfluorides, such as H2SiF6, KHF2, or HBF4, can be added to the cleaner coater composition to supply free fluorides. Those skilled in the art will understand that the presence of free fluorides in the cleaner coater bath can affect zirconium deposition and substrate etching, and therefore measuring these bath parameters is important. The level of free fluorides depends on the pH and the chelating agents added to the cleaner coater bath, and indicates the degree of fluoride binding to metal ions / protons present in the cleaner coater bath.

[0060] The total fluoride content of the cleaner coater composition may be at least 60 ppm based on the total weight of the cleaner coater composition, for example, at least 125 ppm, for example, at least 200 ppm, for example, at least 250 ppm. The total fluoride content of the cleaner coater composition may be 10,000 ppm or less based on the total weight of the cleaner coater composition, for example, 7,500 ppm or less, for example, 5,000 ppm or less, for example, 3,000 ppm or less, for example, 2,500 ppm or less. The total fluoride content of the cleaner coater composition may be 60 ppm to 10,000 ppm based on the total weight of the cleaner coater composition, for example, 125 ppm to 7,500 ppm, for example, 200 ppm to 5,000 ppm, for example, 250 ppm to 3,000 ppm, for example, 250 ppm to 2,500 ppm.

[0061] Free fluoride in the cleaner coater composition may be present in an amount of at least 25 ppm, for example, at least 35 ppm, or for example, at least 50 ppm, based on the total weight of the cleaner coater composition. Free fluoride in the cleaner coater composition may be present in an amount of 750 ppm or less, for example, 600 ppm or less, or for example, 500 ppm or less, based on the total weight of the cleaner coater composition. Free fluoride in the cleaner coater composition may be present in an amount of 25 ppm to 750 ppm, for example, 35 ppm to 600 ppm, or for example, 50 ppm to 500 ppm, based on the total weight of the cleaner coater composition.

[0062] The cleaner coater composition may optionally further contain lithium. The source of lithium metal in the cleaner coater composition may 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.

[0063] Lithium may be present in the cleaner coater composition in an amount of at least 2 ppm based on the total weight of the cleaner coater composition, for example, at least 5 ppm, for example, at least 25 ppm, for example, at least 75 ppm. Lithium may be present in the cleaner coater composition in an amount of 1,000 ppm or less based on the total weight of the cleaner coater composition, for example, 500 ppm or less, for example, 250 ppm or less, for example, 125 ppm or less, for example, 100 ppm or less. Lithium may be present in the cleaner coater composition in an amount of 2 ppm to 1,000 ppm based on the total weight of the cleaner coater composition, for example, 5 ppm to 500 ppm, for example, 5 ppm to 250 ppm, for example, 25 ppm to 125 ppm, for example, 75 ppm to 125 ppm, for example, 75 ppm to 100 ppm.

[0064] The cleaner coater composition may optionally contain molybdenum. The source of molybdenum in the cleaner coater composition may 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.

[0065] Molybdenum may be present in the cleaner coater composition in an amount of at least 5 ppm based on the total weight of the cleaner coater composition, for example, at least 25 ppm, for example, at least 50 ppm, for example, at least 100 ppm. Molybdenum may be present in the cleaner coater composition in an amount of 5,000 ppm or less based on the total weight of the cleaner coater composition, for example, 2,500 ppm or less, for example, 500 ppm or less, for example, 250 ppm or less, for example, 150 ppm or less. Molybdenum may be present in the cleaner coater composition in an amount of 5 ppm to 5,000 ppm based on the total weight of the cleaner coater composition, for example, 25 ppm to 2,500 ppm, for example, 50 ppm to 500 ppm, for example, 25 ppm to 250 ppm, for example, 100 ppm to 150 ppm.

[0066] The cleaner coater composition may contain a pH of at least 1.0, for example, at least 1.5, for example, at least 2.0, for example, at least 3.0, for example, at least 3.5, for example, at least 4.0. The cleaner coater composition may contain a pH of 6.0 or less, for example, at least 5.5, for example, at least 5.0, for example, at least 4.5, for example, at least 3.5. The cleaner coater composition may contain a pH in the range of 1.0 to 6.0, for example, at least 1.5 to 6.0, for example, at least 2.0 to 5.0, for example, at least 3.0 to 5.0, for example, at least 1.0 to 5.0, for example, at least 1.5 to 4.5, for example, at least 2.0 to 3.5, for example, at least 4.0 to 6.0, for example, at least 4.0 to 5.5, for example, at least 4.0 to 5.0. The pH values ​​described herein can be measured under ambient conditions using a pH meter (Interface, DualStar pH / ISEDual Channel Benchtop Meter, ThermoFisher Scientific, available from Weytham, Massachusetts, USA) and a pH probe (ACCUMET pH probe (Ag / AgCl reference electrode) from Fisher Scientific). The pH of the cleaner coater composition may be maintained by including an acidic material containing water-soluble and / or water-dispersible acids such as nitric acid, sulfuric acid, and / or phosphoric acid. The pH of the cleaner coater composition may be maintained by including a basic material containing water-soluble and / or water-dispersible bases (sodium hydroxide, sodium carbonate, potassium hydroxide, ammonium hydroxide, ammonia, and / or amines such as triethylamine, methylethylamine, or mixtures thereof).

[0067] The cleaner coater composition may, in some cases, prevent the formation of phosphate ions or phosphate-containing compounds, such as aluminum phosphate, iron phosphate, and / or zinc phosphate, and / or sludge, which may be formed when a zinc phosphate-based treatment agent is used. As used herein, “phosphate-containing compound” includes, but is not limited to, compounds containing the element of phosphorus, such as orthophosphate, pyrophosphate, metaphosphate, and tripolyphosphate, and may contain monovalent, divalent, or trivalent cations, such as sodium, potassium, calcium, zinc, nickel, manganese, aluminum, and / or iron. If the material deposited on the substrate surface by the deposition of the composition and / or cleaner coater composition is substantially phosphate-free, essentially phosphate-free, or completely phosphate-free, this includes compounds containing any form of phosphate ions or phosphoric acid.

[0068] Therefore, cleaner coater compositions and / or coatings deposited on a substrate surface by the deposition of cleaner coater compositions may be substantially, in some cases essentially, or in some cases completely free of one or more of the ions or compounds listed in the preceding paragraphs. A cleaner coater composition and / or coating that is substantially phosphate-free means that phosphate ions or compounds containing phosphate are not intentionally added, but may be present in trace amounts due to impurities or unavoidable environmental contamination. In other words, the amount of material is so small that it does not affect the properties of the composition. This may include the absence of phosphate in the cleaner coater composition and / or deposited material at levels that would burden the environment. The term "substantially free" means that the cleaner coater composition and / or coating contains, if any, any or all of the phosphate anions or compounds enumerated in the preceding paragraphs, based on the total weight of the composition or deposited material, in amounts less than 5 ppm. The term "essentially free" means that the cleaner coater composition and / or coating contains any or all of the phosphate anions or compounds described in the preceding paragraphs in amounts less than 1 ppm. The term "completely free" means that the cleaner coater composition and / or coating contains, if any, any or all of the phosphate anions or compounds described in the preceding paragraph, in amounts less than 1 ppb.

[0069] Cleaner coater compositions may exclude chromium or chromium-containing compounds. That is, cleaner coater compositions and / or coatings deposited from cleaner coater compositions may be substantially chromium-free, essentially chromium-free, and / or completely chromium-free. As used herein, the term “chromium-containing compound” refers to materials containing trivalent and / or hexavalent chromium. Non-limiting examples of such materials include chromic acid, chromium trioxide, chromic anhydride, dichromate salts, e.g., ammonium dichromate, sodium dichromate, potassium dichromate, and dichromate salts of calcium, barium, magnesium, zinc, cadmium, strontium, chromium(III) sulfate, chromium(III) chloride, and chromium(III) nitrate. If a cleaner coater composition or a coating deposited by a cleaner coater composition is substantially chromium-free, essentially chromium-free, or completely chromium-free, this includes, but is not limited to, all forms of chromium, including the trivalent and hexavalent chromium-containing compounds listed above.

[0070] Therefore, selectively, cleaner coater compositions and / or coatings may substantially, essentially, and / or completely be free of any one or more of the elements or compounds mentioned in the preceding paragraph. A cleaner coater composition or coating substantially free of chromium or its derivatives means that chromium or its derivatives are not intentionally added, but may be present in trace amounts due to impurities or unavoidable environmental contamination. In other words, the amount of material is so small that it does not affect the properties of the cleaner coater composition or coating. In the case of chromium, this may further include the absence of the element or its compounds in the cleaner coater composition and / or coating at levels that would burden the environment. The term "substantially free" means that the cleaner coater composition and / or coating contains, if any, any or all of the elements or compounds enumerated in the preceding paragraph, based on the total weight of the composition or coating, in amounts less than 10 ppm. The term "essentially free" means that the cleaner coater composition and / or coating contains, if any, any or all of the elements or compounds described in the preceding paragraph, in amounts less than 1 ppm. The term "completely free" means that the cleaner coater composition and / or coating contains 0 ppm of such material, or that such material is below the detection limit of common analytical techniques.

[0071] The cleaner coater composition may contain an aqueous medium and may optionally contain other materials, such as auxiliary materials conventionally used in the field of pretreatment compositions. The aqueous composition may contain a water-dispersible organic solvent, such as methanol or isopropanol, which have up to about eight carbon atoms, or a glycol ether, such as a monoalkyl ether of ethylene glycol, diethylene glycol, or propylene glycol. If present, the water-dispersible organic solvent is typically used up to about 10% of the total volume of the aqueous composition.

[0072] The cleaner coater composition may also include a resin binder. Suitable resins include reaction products of epoxy functional materials comprising one or more alkanolamines and at least two epoxy groups, such as those described in U.S. Patent No. 5,653,823. In some cases, such resins include beta-hydroxyester, imide, or sulfide functionalities, which are incorporated during the preparation of the resin by using dimethylolpropionic acid, phthalimide, or mercaptoglycerin as additional reactants. Alternatively, the reaction product is a reaction product in which the molar ratio of diglycidyl ether of bisphenol A (EPON880, commercially available from Shell Chemical Company), dimethylolpropionic acid, and diethanolamine is 0.6 to 5.0:0.05 to 5.5:1. Other suitable resin binders include water-soluble and water-dispersible polyacrylic acids disclosed in U.S. Patents 3,912,548 and 5,328,525, phenol-formaldehyde resins described in U.S. Patent 5,662,746, water-soluble polyamides disclosed in International Publication 95 / 33869, copolymers of maleic acid or acrylic acid with allyl ethers described in Canadian Patent Application 2,087,352, and water-soluble and dispersible resins including epoxy resins, aminoplasts, phenolic resins, tannins, and polyvinylphenols discussed in U.S. Patent 5,449,415.

[0073] The resin binder may commonly be present in the cleaner coater composition at a weight of 0.005 to 30 percent, for example, 0.5 to 3 percent, based on the total weight of the components of the cleaner coater composition.

[0074] The cleaner coater composition may be substantially free of any resin binder, or in some cases, completely free of any resin binder. As used herein, the term “substantially free” means that any resin binder is present in the cleaner coater composition in trace amounts of less than 0.005 percent when used in the sense that no resin binder is present in the cleaner coater composition. As used herein, the term “completely free” means that no detectable resin binder is present in the cleaner coater composition.

[0075] The cleaner coater composition may be substantially, essentially, or completely free of sodium nitrobenzenesulfonate.

[0076] Electrodeposition coating composition As described above, the system for processing the substrate includes an electrodepositable coating composition.

[0077] As used herein, the term “electrodepositionable coating composition” refers to a composition that can be deposited on an electrically conductive substrate while being affected by a potential applied between two electrodes immersed in the electrodepositionable coating composition, where one electrode is the substrate to be coated.

[0078] Electrodeposition coating compositions include an electrodeposition binder. For example, the electrodeposition binder may include organic and / or inorganic electrodeposition binders. As used herein, the term “binder” refers to the non-volatile components of an electrodeposition coating composition, excluding fillers.

[0079] As used herein, “organic” electrodeposition binders refer to film-forming polymers having a skeletal structure containing carbon atoms in their backbone. As used herein, “inorganic” electrodeposition binders refer to film-forming polymers having a skeletal structure that does not contain carbon atoms in their backbone, such as silicone-based materials. It should be understood that electrodeposition binders may also include mixtures of organic and inorganic film-forming and / or curing agent materials.

[0080] As used herein, the term “film-forming polymer” is used synonymously with “polymer” or “resin” and refers to one or more polymers, including homopolymers and / or copolymers, as well as prepolymers, oligomers, monomers, etc., that can form a coating by reaction with a curing agent or crosslinking agent. As used herein, the terms “crosslinked material,” “crosslinking agent,” or “curing agent” refer to molecules that can form covalent bonds between polymers. For example, a polyisocyanate curing agent can react with active hydrogen groups on a film-forming polymer to cure a coating composition and form a coating. As used herein, “cured,” “cured,” or similar terms mean that a portion of the coating composition has been crosslinked to form a coating.

[0081] The electrodepositable coating composition may contain an ionic base-containing film-forming polymer, such as a cationic base-containing film-forming polymer or an anionic base-containing film-forming polymer.

[0082] For example, an ionic base-containing film-forming polymer may include a reaction product of a reactant comprising (a) a polyepoxide, (b) a bifunctional chain extender, and (c) a monofunctional reactant. Non-limiting examples of such polymers are provided in paragraphs

[0023] to

[0038] of International Application PCT / US22 / 73356, the portions cited herein are incorporated by reference.

[0083] As used herein, the term “cationic base-containing film-forming polymer” refers to a polymer containing at least partially neutralized cationic bases, such as amines, sulfonium and / or ammonium bases, that impart a positive charge. Cationic base-containing film-forming polymers may contain active hydrogen functional groups. As used herein, the term “active hydrogen functional group” refers to a functional group that reacts with isocyanates, such as hydroxyl groups, primary or secondary amine groups, carbamates, thiol groups, and the like.

[0084] Examples of non-limiting polymers suitable for use as cationic base-containing film-forming polymers in electrodepositable coating compositions include, but are not limited to, alkyd polymers, acrylics, polyepoxides, polyamides, polyurethanes, polyureas, polyethers, polyesters, and their adducts, derivatives, and combinations.

[0085] Cationic base-containing film-forming polymers can be made positive and water-dispersible by at least partial neutralization with acids such as formic acid, acetic acid, methanesulfonic acid, lactic acid, phosphoric acid, and / or sulfamic acid.

[0086] The degree of neutralization of cationic base-containing film-forming polymers may vary depending on the specific polymer involved. However, sufficient acid must be used to neutralize the cationic base-containing film-forming polymers so that they can be dispersed in an aqueous dispersion medium. For example, the amount of acid used may provide at least 20% of the total theoretical neutralization. Alternatively, the amount of acid used may provide more than 100% of the total theoretical neutralization. The total amount of acid used to neutralize cationic base-containing film-forming polymers can be any combination of values ​​in the range of, for example, 20% or more and more than 100%, including the values ​​described. For example, the total amount of acid used to neutralize an active hydrogen-containing cationic base-containing film-forming polymer may be 20%, 35%, 50%, 60%, 80%, or more than 100%, based on the total amount of amines in the cationic base-containing film-forming polymer.

[0087] As used herein, the term “anionic base-containing film-forming polymer” refers to an anionic polymer containing at least partially neutralized anionic functional groups, such as carboxylic acids and / or phosphate groups that impart a negative charge. Anionic base-containing film-forming polymers may also contain active hydrogen functional groups.

[0088] Non-limiting examples of polymers suitable for use as anionic base-containing film-forming polymers for electrodeposition binders include, but are not limited to, dry or semi-dry and / or saturated alkyd polymers, acrylics, polyepoxides, polyamides, polyurethanes, polyureas, polyethers, polyesters, resinous polyols, phosphorylated polyepoxides, phosphorylated acrylic polymers, alkyds and amine-aldehyde vehicles, as well as adducts, derivatives and combinations thereof.

[0089] Non-limiting examples of inorganic electrodepositable film-forming polymers include silicone-based film-forming polymers. Non-limiting examples of such polymers are described in paragraphs

[0007] to

[0029] of International Publication No. 2021 / 138384A1, the cited portions of which are incorporated herein by reference.

[0090] The ionic base-containing film-forming polymer may be present in the electrodepositable coating composition in an amount of at least 40% by weight, for example, at least 50% by weight, for example, at least 55% by weight, for example, at least 60% by weight, based on the total weight of the resin solids of the electrodepositable coating composition. The ionic base-containing film-forming polymer may be present in the electrodepositable coating composition in an amount of 90% by weight or less, for example, 80% by weight or less, for example, 75% by weight or less, based on the total weight of the resin solids of the electrodepositable coating composition. The ionic base-containing film-forming polymer may be present in the electrodepositable coating composition in amounts of 40% to 90% by weight, for example 40% to 80% by weight, for example 40% to 75% by weight, for example 50% to 90% by weight, for example 50% to 80% by weight, for example 50% to 75% by weight, for example 55% to 90% by weight, for example 55% to 80% by weight, for example 55% to 75% by weight, for example 60% to 90% by weight, for example 60% to 80% by weight, for example 60% to 75% by weight, based on the total weight of the resin solids in the electrodepositable coating composition.

[0091] As used herein, “resin solids” includes an ionic base-containing film-forming polymer, a curing agent, and additional water-dispersible non-pigment components present in the electrodeposited coating composition.

[0092] The electrodepositable coating compositions of this disclosure may further include a curing agent. The curing agent may react with the ionic base-containing film-forming polymer and, if present, with the reactive groups of additional resin materials, such as active hydrogen groups, to cure the electrodepositable coating composition and form a coating. Non-limiting examples of suitable curing agents include partially or completely blocked polyisocyanates, as well as aminoplast resins and / or phenolplast resins, such as phenol-formaldehyde condensates containing allyl ethers and their derivatives.

[0093] As used herein, “blocked polyisocyanate” means a polyisocyanate in which at least some of the isocyanate groups are blocked by blocking groups introduced by the reaction of the free isocyanate groups of the polyisocyanate with a blocking agent. “Blocked” means that the isocyanate groups are reacted with a blocking agent, and the resulting blocked isocyanate groups are stable with respect to active hydrogen at ambient temperature, for example, room temperature (23°C). This reaction can be reversed under suitable conditions, for example, high temperatures between 90°C and 200°C, thereby deblocking the previously blocked isocyanate groups of the polyisocyanate curing agent, which can then react with the reactive groups of the ionic base-containing film-forming polymer, for example, active hydrogen groups, thereby curing the coating composition and forming a coating.

[0094] Blocking agents that dissociate from the blocking polyisocyanate curing agent during curing can be removed from the coating by volatilization. Alternatively, at least some of the blocking agent may remain in the coating after curing.

[0095] Suitable polyisocyanates, as well as blocking components such as blocking groups and / or blocking agents, for example, 1,2-polyols, etc., non-limiting examples of blocking polyisocyanate curing agents and their amounts are provided in paragraphs

[0022] to

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

[0096] Non-limiting examples of blocked polyisocyanates containing blocking groups obtained from blocking agents comprising α-hydroxyamides, esters, or thioesters, and optionally including a second blocking agent, are shown in paragraphs

[0010] to

[0029] of International Publication No. 2018 / 148306A1, the cited portions of which are incorporated herein by reference. A blocked polyisocyanate may be a fully blocked polyisocyanate in which essentially 100% of the isocyanate groups of the polyisocyanate are blocked by one or more blocking groups. Optionally, a blocked polyisocyanate curing agent may be a at least partially blocked polyisocyanate in which less than 100% of the isocyanate groups are blocked, as long as the coating composition remains a stable dispersion.

[0097] At least partially blocked polyisocyanates are partially blocked by one or more blocking groups as discussed above, and the remaining isocyanate groups react with the polymer backbone as described in U.S. Patent No. 3,947,338, row 65 of column 2 to row 33 of column 5, the cited portion incorporated herein by reference.

[0098] The blocked polyisocyanate curing agent may contain 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-ethylhexycarbonylamino)-1,3,5-triazine, and combinations thereof.

[0099] The curing agent may contain an aminoplast or phenoplast resin. An aminoplast resin is a condensation product of an aldehyde and a substance containing an amino or amide group. A phenoplast resin is formed by the condensation of an aldehyde and a phenol.

[0100] Non-limiting examples of commercially available aminoplast resins include those available under the trademark CYMEL® of Allnex Belgium SA / NV, such as CYMEL 1130 and 1156, and those available under the trademark RESIMENE® from INEOS Melamines, such as RESIMENE 750 and 753. Examples of suitable aminoplast resins and their quantities also include those described in columns 16, row 3 to 17, row 47 of U.S. Patent No. 3,937,679, which are incorporated by reference. As disclosed in the aforementioned portion of U.S. Patent No. 3,937,679, aminoplasts may be used in combination with methylolphenol ethers.

[0101] Suitable aminoplast and phenoplast resins are also described in U.S. Patent No. 4,812,215, column 6, row 20 to column 7, row 12, the cited portion of which is incorporated herein by reference.

[0102] Non-limiting examples of additional curing agents include silicone-based curing agents. Non-limiting examples of such curing agents are described in paragraphs

[0030] to {0043} of International Publication No. 2021 / 138384A1, the quoted portions of which are incorporated herein by reference.

[0103] The curing agent may be present in the electrodeposited coating composition in an amount of at least 10% by weight, for example, at least 20% by weight, or for example, at least 25% by weight, based on the total weight of the resin solids in the electrodeposited coating composition. The curing agent may be present in the electrodeposited coating composition in an amount of 60% by weight or less, for example, 50% by weight or less, for example, 45% by weight or less, or for example, 40% by weight or less, based on the total weight of the resin solids in the electrodeposited coating composition. The curing agent may be present in the electrodepositable coating composition in an amount of 10% to 60% by weight, for example 10% to 50% by weight, for example 10% to 45% by weight, for example 10% to 40% by weight, for example 20% to 60% by weight, for example 20% to 50% by weight, for example 20% to 45% by weight, for example 20% to 40% by weight, for example 25% to 60% by weight, for example 25% to 50% by weight, for example 25% to 45% by weight, for example 25% to 40% by weight, based on the total weight of the resin solids content of the electrodepositable coating composition.

[0104] The electrodeposited coating composition further comprises a curing catalyst. As used herein, the term “curing catalyst” is used synonymously with “catalyst” and refers to a substance that does not undergo a permanent chemical change itself, but increases the rate of a chemical reaction or decreases the activation energy of a reaction. For example, a catalyst may catalyze a transurethane reaction, specifically the deblocking of blocking groups in a blocked polyisocyanate.

[0105] 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.

[0106] Suitable catalysts for cationic electrodeposition coating compositions include, but are not limited to, metal oxides (e.g., oxides of cerium, zirconium, and bismuth) and their salts, zinc compounds or complexes, and / or cyclic guanidines as described in U.S. Patent No. 7,842,762, column 1, row 53 to column 4, row 18, column 16, row 62 to column 19, row 8, the cited portions of which are incorporated herein by reference.

[0107] Suitable catalysts for anionic electrodeposition coating compositions include, without limitation, latent acid catalysts. Latent acid catalysts are generally derivatives of acid catalysts that are activated by heating. Non-limiting examples of latent acid catalysts are identified in paragraph

[0031] of International Publication No. 2007 / 118024. 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.

[0108] The amine-containing curing catalyst may include, but is not limited to, any suitable amine-containing curing catalyst, including guanidine, imidazole, amidine, and their derivatives or combinations.

[0109] Non-limiting examples of suitable guanidine curing catalysts are provided in International Publication No. 2018 / 0172519A1, paragraphs

[0039] to

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

[0110] Non-limiting examples of imidazole curing catalysts are described in paragraphs

[0062] to

[0108] of U.S. Publication No. 2022 / 0154014A1, the cited portions of which are incorporated herein by reference.

[0111] Amidine curing catalysts may, in non-limiting examples, include 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU).

[0112] Zinc-containing catalysts may include metal salts and / or zinc complexes, including, but are not limited to, zinc(II) amidine complexes, zinc octanoate, zinc naphthenate, zinc tolate, zinc carboxylates having 8 to 14 carbon atoms in the carboxyl group, zinc acetate, zinc sulfate, zinc methanesulfonate, or any combination thereof. Zinc(II) amidine complexes may include amidine and carboxylate ligands.

[0113] The curing catalyst may include a bismuth catalyst. Non-limiting examples of bismuth curing catalysts and their quantities are provided in paragraphs

[0036] to

[0050] of International Publication No. 2021 / 138583A1, and the quoted portions are incorporated herein by reference.

[0114] The curing catalyst is, for example, Ti(OR 1 )4 may contain titanium compounds and / or complexes, where R 1 is alkyl or aryl, for example R 1 The C3-C20 alkyl group is such as tetrabutyl titanate, R 1 Examples include n-butyl.

[0115] The curing catalyst may be present in the electrodepositable coating composition in any suitable amount. For example, an amine and / or zinc-containing curing catalyst may be present in the coating composition in an amount of at least 0.1% by weight, e.g., at least 0.2% by weight, e.g., at least 0.5% by weight, e.g., at least 0.8% by weight, e.g., at least 1% by weight, e.g., at least 1.5% by weight, based on the total weight of the resin solids in the coating composition. The amine and / or zinc-containing curing catalyst may be present in the coating composition in an amount of 7% by weight or less, e.g., 4% by weight or less, e.g., 2% by weight or less, e.g., 1.5% by weight or less, e.g., 1% by weight or less, based on the total weight of the resin solids in the coating composition. The amine and / or zinc-containing curing catalyst is present in amounts of 0.1% to 7% by weight, for example 0.1% to 4% by weight, for example 0.1% to 2% by weight, for example 0.1% to 1.5% by weight, for example 0.1% to 1% by weight, for example 0.2% to 7% by weight, for example 0.2% to 4% by weight, for example 0.2% to 2% by weight, for example 0.2% to 1.5% by weight, for example 0.2% to 1% by weight, for example 0.5% to 7% by weight, for example 0.5% to 4% by weight, for example 0.5% by weight It may be present in the coating composition in amounts of %~2% by weight, for example 0.5%~1.5% by weight, for example 0.5%~1% by weight, for example 0.8%~7% by weight, for example 0.8%~4% by weight, for example 0.8%~2% by weight, for example 0.8%~1.5% by weight, for example 0.8%~1% by weight, for example 1%~7% by weight, for example 1%~4% by weight, for example 1%~2% by weight, for example 1%~1.5% by weight, for example 1.5%~7% by weight, for example 1.5%~4% by weight, for example 1.5%~2% by weight.

[0116] Electrodeposition coating compositions may be substantially, essentially, or completely tin-free of catalytic tin. As used herein, an electrodeposition coating composition is "substantially tin-free" if catalytic tin is present in an amount of less than 0.1% by weight based on the total weight of the electrodeposition coating composition. As used herein, an electrodeposition coating composition is "essentially tin-free" if catalytic tin is present in an amount of less than 0.01% by weight based on the total weight of the electrodeposition coating composition. As used herein, an electrodeposition coating composition is "completely tin-free" if catalytic tin is present in an amount of less than 0.001% by weight based on the total weight of the electrodeposition coating composition.

[0117] The electrodepositable coating composition may further optionally include a polymer containing at least one phosphorylation group. This polymer is not limited. Non-limiting examples of polymers include addition polymers containing at least one phosphorylation group, phosphate-treated epoxy resins, and other polymers containing at least one phosphorylation group.

[0118] The phosphorous acid equivalent of the polymer can be at least 0.01 milliequivalent per gram of the polymer, for example at least 0.05, for example at least 0.1, for example at least 1, for example at least 2, for example at least 4 milliequivalents. The phosphorous acid equivalent of the polymer can be 10 milliequivalents or less per gram of the polymer, for example 7 or less, for example 5 or less, for example 3 or less, for example 2 or less, for example 1 or less. The phosphorous acid equivalent of the polymer can be 0.01 - 10 milliequivalents per gram of the polymer, for example 0.01 - 7, for example 0.01 - 5, for example 0.01 - 3, for example 0.01 - 2, for example 0.01 - 1, for example 0.05 - 10, for example 0.05 - 7, for example 0.05 - 5, for example 0.05 - 3, 0.05 - 2, for example 0.05 - 1, for example 0.1 - 10, for example 0.1 - 7, for example 0.1 - 5, for example 0.1 - 3, for example 0.1 - 2, for example 0.1 - 1, for example 1 - 10, for example 1 - 7, for example 1 - 5, for example 1 - 3, for example 1 - 2, for example 2 - 10, for example 2 - 7, for example 2 - 5, for example 2 - 3, for example 4 - 10, for example 4 - 7, for example 4 - 5. The phosphorous acid equivalent can be determined by dividing the total weight of the polymer by the total number of phosphorous acid groups present in the polymer.

[0119] As used herein, the terms "phosphorylated group" and "phosphorous acid group" refer to phosphate groups bonded to the polymer. As used herein, "phosphate" has the general chemical formula [PO4] 3- , [HPO4] 2- , and / or [H2PO4] - and refers to an anion derived from phosphoric acid having. Although "phosphate" ions are referred to herein, derivatives of other phosphoric acid derivatives are also included within the scope of the disclosure. Thus, unless otherwise specified, phosphate ions may refer to phosphonate anions derived from phosphonic acids having the general chemical formula [RPO3] 2- and / or [RHPO3] 1- and phosphinate anions derived from phosphinic acids.

[0120] Polymers containing at least one phosphorylated group can include addition polymers.

[0121] As used herein, the term “addition polymer” refers to a polymerization product formed by the polymerization reaction of monomers in a monomer composition to form a polymer. After polymerization of the monomers in the monomer composition, the addition polymer contains constituent units corresponding to each residue of the polymerized monomer. As used herein, the term “residue of” when referring to a polymer composition refers to a single molecular unit (i.e., constituent unit) within the polymer resulting from the incorporation (i.e., reaction) of monomers during polymerization. Addition polymers are formed by polymerizing a monomer composition containing ethylenically unsaturated monomers.

[0122] The monomer composition contains a phosphite-functional monomer. The phosphite group may include a phosphonic acid group, a phosphinic acid group, or a combination thereof, as well as salts thereof. The ethylene-unsaturated phosphite-functional monomer may be a dihydrogen phosphate ester of an alcohol containing or substituted with a polymerizable vinyl or olefin group in the alcohol. Suitable ethylene-unsaturated phosphite-functional monomers 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, R p=alkyl, n is a number from 1 to 20, and may include, for example, SIPOMER PAM-100, SIPOMER PAM-200, SIPOMER PAM-300, SIPOMER PAM-4000 available from Solvay, phosphoalkoxy (meth)acrylates such as phosphoethylene glycol (meth)acrylate, phosphodiethylene glycol (meth)acrylate, phosphotriethylene glycol (meth)acrylate, phosphopropylene glycol (meth)acrylate, phosphodipropylene glycol (meth)acrylate, phosphotripropylene glycol (meth)acrylate, phosphotripropylene glycol (meth)acrylate, salts thereof, and mixtures thereof. The phosphite functional monomer may be present in the monomer composition in an amount of at least 0.1% by weight, e.g., at least 1% by weight, e.g., at least 2% by weight, based on the total weight of the monomer composition. The phosphite functional monomer may be present in the monomer composition in an amount of 20% by weight or less, e.g., 10% by weight or less, e.g., 8% by weight or less, based on the total weight of the monomer composition. The phosphite functional monomer may be present in the monomer composition in amounts of 0.1% to 20% by weight, for example, 0.1% to 10% by weight, for example, 0.1% to 8% by weight, for example, 1% to 20% by weight, for example, 1% to 10% by weight, for example, 1% to 8% by weight, for example, 2% to 20% by weight, for example, 2% to 10% by weight, for example, 2% to 8% by weight, based on the total weight of the monomer composition.

[0123] The monomer composition and the resulting addition polymer may further contain at least one other ethylenically unsaturated monomer. For example, the monomer composition and the resulting addition polymer may contain C1-C12. 18 The materials may further include alkyl (meth)acrylate monomers, hydroxyl functional (meth)acrylate monomers, vinyl aromatic compounds, monomers containing two or more ethylenically unsaturated groups per molecule, (meth)acrylamide monomers, monoalkyl (meth)acrylamide monomers, dialkyl (meth)acrylamide monomers, and / or hydroxyl functional (meth)acrylamide monomers.

[0124] As used herein, “(meth)acrylate” or “(meth)acrylamide” and similar terms include both acrylate and methacrylate or both acrylamide and methacrylamide, respectively.

[0125] Electrodeposition coating compositions may further contain pigments. Non-limiting examples of pigments include, for example, iron oxide, lead oxide, strontium chromate, carbon black, charcoal dust, titanium dioxide, talc, barium sulfate, thermally conductive electrical insulating fillers, thermally conductive conductive fillers, non-thermally conductive electrical insulating fillers, flame retardant pigments, and color pigments such as cadmium yellow, cadmium red, and chromium yellow. As used herein, “electrically insulating filler” means a pigment, filler, or inorganic powder having a volume resistivity of at least 10 Ω·m (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 Ω·m (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 (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 (measured according to ASTM D7984).

[0126] The pigments may include plate-like pigments, such as inorganic plate-like pigments.

[0127] Plate-like pigments can be phyllosilicate pigments. As used herein, the term "phyllosilicate" refers to SiO4 that spreads outward as an infinite sheet. -4 This refers to a group of minerals that have silicate sheets with a basic structure based on interconnected tetrahedral 6-membered rings, where three of the four oxygen atoms in each tetrahedron are shared with other tetrahedrons, and phyllosilicate has Si2O5 as its basic structural unit. -2This will result in the presence of a hydroxide ion located at the center of the tetrahedron, and / or, for example, Fe +2 Mg +2 , or Al +3 These pigments may contain cations such as , which form a cation layer between silicate layers, and the cations may coordinate with oxygen and / or hydroxide ions in the silicate layer. The term "phyllosilicate pigment" refers to pigment materials containing phyllosilicate. Non-limiting examples of phyllosilicate pigments include mica, chlorite, serpentine, talc, and clay minerals. Clay minerals include, for example, kaolin clay. The sheet-like structure of phyllosilicate pigments is such that the pigments tend to have a plate-like structure, but the pigments can be manipulated (through mechanical means, etc.) to have other particulate structures. These pigments may or may not swell when exposed to a liquid medium, and may or may not contain soluble components (e.g., ions attracted to the liquid medium).

[0128] Plate-like pigments may include plate-like mica pigments, plate-like chlorite pigments, plate-like serpentine pigments, plate-like talc pigments, and / or plate-like clay pigments. Plate-like clay pigments may include kaolin clay, consist essentially of kaolin clay, or consist of kaolin clay.

[0129] Pigment components containing plate-like pigments may have an average equivalent spherical diameter of at least 50 nm, up to 25 microns or more. The average equivalent spherical diameter can be determined by dynamic light scattering using a SEDIGRAPH III PLUS particle size analyzer available from Micromeritics Instrument Corp. As plate-like particles, pigments often have substantially opposing surfaces, and the particles typically exhibit an aspect ratio of longest axis to shortest axis of at least 2:1, e.g., at least 4:1, e.g., at least 6:1, e.g., at least 8:1, e.g., at least 10:1 or more. For example, plate-like pigments may have an average equivalent spherical diameter of at least 50 nm, e.g., at least 0.2 microns, e.g., at least 0.4 microns, e.g., at least 0.6 microns, e.g., at least 1 micron, e.g., at least 2 microns, e.g., at least 3 microns, e.g., at least 4 microns, e.g., at least 5 microns. The plate-shaped pigment may have an average spherical equivalent diameter of 25 microns or less, for example, 15 microns or less, for example, 10 microns or less, for example, 5 microns or less, for example, 3.5 microns or less, for example, 2.5 microns or less, for example, 1.9 microns or less, for example, 1.5 microns or less, for example, 1 micron or less.

[0130] The pigment-to-binder ratio (P:B ratio) described herein may refer to the weight ratio of pigment to binder in an electrodepositable coating composition. The pigment-to-binder ratio (P:B ratio) of pigment to electrodepositable binder may be at least 0.05:1, for example at least 0.1:1, for example at least 0.2:1, for example at least 0.3:1, for example at least 0.35:1, for example at least 0.4:1, for example at least 0.5:1, for example at least 0.6:1, for example at least 0.67, for example at least 0.7:1, for example at least 0.75:1, for example at least 1:1, for example at least 1.25:1, for example at least 1.5:1. The ratio of pigment to electrodepositing binder (P:B ratio) may be 2:1 or less, for example 1.75:1 or less, for example 1.5:1 or less, for example 1.25:1 or less, for example 1:1 or less, for example 0.75:1 or less, for example 0.7:1 or less, for example 0.6:1 or less, for example 0.55:1 or less, for example 0.5:1 or less, for example 0.25:1 or less. The pigment-to-binder ratio (P:B ratio) is typically 0.05:1 to 2:1, e.g., 0.05:1 to 1:1, e.g., 0.05:1 to 0.75:1, e.g., 0.05:1 to 0.7:1, e.g., 0.05:1 to 0.6:1, e.g., 0.05:1 to 0.55:1, e.g., 0.05:1 to 0.5:1, e.g., 0.05 to 0.25:1, e.g., 0.1:1 to 2:1, e.g., 0.1:1 to 1:1, e.g., 0.1:1 to 0.75:1, e.g., 0.1:1 to 0.7:1, e.g., 0.1:1 to 0.6:1, e.g., 0.1:1 to 0.55:1, e.g., 0.1:1 to 0.5:1, e.g., 0.1:1 to 0.25:1, e.g., 0.2:1 to 0.55:1, e.g., 0.1 2:1, for example 0.2:1~1:1, for example 0.2:1~0.75:1, for example 0.2:1~0.7:1, for example 0.2:1~0.6:1, for example 0.2:1~0.55:1, for example 0.2:1~0.5:1, for example 0.2:1~0.25:1, for example 0.3:1~2:1, for example 0.3:1~1:1, for example 0.3:1~0.75:1, for example 0.3:1~0.7:1, for example 0.3:1~0.6:1, for example 0.3:1~0.55:1, for example 0.3:1~0.5:1, for example 0.4:1~2:1, for example 0.4:1~1.75:1, for example 0.4:1~1.5:1, for example 0.4:1~1.25:1, for example 0.4:1~1:1, for example 0.4:1~0.75:1, for example 0.4:1~0.7:1, for example 0.4:1~0.6:1, for example 0.4:1~0.55:1, for example 0.4:1~0.5:1, for example 0.5:1~2:1, for example 0.5:1~1.75:1, for example 0.5:1~1.50:1, for example 0.5:1~1.25:1, for example 0.5:1~1:1, for example 0.5:1~0.75:1, for example 0.5:1~ 0.7:1, for example 0.5:1~0.6:1, for example 0.5:1~0.55:1, for example 0.6:1~2:1, for example 0.6:1~1.75:1, for example 0.6:1~1.5:1, for example 0.6:1~1.25:1, for example 0.6:1~1:1, for example 0.6:1~0.75:1, for example 0.6:1~0.7:1, for example 0.67:1~2:1, for example 0.67:1~1.75:1, for example 0.67:1~1. 5:1, for example 0.67:1~1.25:1, for example 0.67:1~1:1, for example 0.67:1~0.75:1, for example 0.67:1~0.7:1, for example 0.7:1~2:1, for example 0.7:1~1.75:1, for example 0.7:1~1.5:1, for example 0.7:1~1.25:1, for example 0.7:1~1:1, for example 0.7:1~0.75:1, for example 0.75:1~2:1, for example 0.75:1~1.7 Possible ratios include 5:1, for example 0.75:1~1.5:1, for example 0.75:1~1.25:1, for example 0.75:1~1:1, for example 1:1~2:1, for example 1:1~1.75:1, for example 1:1~1.5:1, for example 1:1~1.25:1, for example 1.25:1~2:1, for example 1.25:1~1.75:1, for example 1.25:1~1.5:1, for example 1.5:1~2:1, and for example 1.5:1~1.75:1.

[0131] The pigment-to-binder ratio (P:B ratio) of inorganic plate-like pigment to electrodeposition binder may be at least 0.4:1, for example at least 0.5:1, for example at least 0.6:1, for example at least 0.75:1, for example at least 1:1, for example at least 1.25:1, for example at least 1.5:1. The pigment-to-binder ratio (P:B ratio) of inorganic plate-like pigment to electrodeposition binder may be 2:1 or less, for example 1.75:1 or less, for example 1.5:1 or less, for example 1.25:1 or less, for example 1:1 or less, for example 0.75:1 or less, for example 0.7:1 or less, for example 0.6:1 or less, for example 0.55:1 or less, for example 0.5:1 or less. The pigment-to-binder ratio (P:B ratio) of inorganic plate-like pigments to electrodepositable binders is typically 0.4:1 to 2:1, for example 0.4:1 to 1.75:1, for example 0.4:1 to 1.5:1, for example 0.4:1 to 1.25:1, for example 0.4:1 to 1:1, for example 0.4:1 to 0.75:1, for example 0.4:1 to 0.7:1, for example 0.4:1 to 0.6:1, for example 0.4:1 to 0.55:1, for example 0.4:1~0.5:1, for example 0.5:1~2:1, for example 0.5:1~1.75:1, for example 0.5:1~1.50:1, for example 0.5:1~1.25:1, for example 0.5:1~1:1, for example 0.5:1~0.75:1, for example 0.5:1~0.7:1, for example 0.5:1~0.6:1, for example 0.5:1~0.55:1, For example, 0.6:1~2:1, for example, 0.6:1~1.75:1, for example, 0.6:1~1.5:1, for example, 0.6:1~1.25:1, for example, 0.6:1~1:1, for example, 0.6:1~0.75:1, for example, 0.6:1~0.7:1, for example, 0.75:1~2:1, for example, 0.75:1~1.75:1, for example, 0.75:1~1.5:1, for example, 0.7 The ratios could be 5:1 to 1.25:1, for example 0.75:1 to 1:1, for example 1:1 to 2:1, for example 1:1 to 1.75:1, for example 1:1 to 1.5:1, for example 1:1 to 1.25:1, for example 1.25:1 to 2:1, for example 1.25:1 to 1.75:1, for example 1.25:1 to 1.5:1, for example 1.5:1 to 2:1, for example 1.5:1 to 1.75:1.

[0132] Electrodeposition coating compositions may optionally contain dispersants to help disperse pigments and other optional fillers.

[0133] Electrodeposition coatings and / or electrodeposition compositions may optionally contain corrosion inhibitors. Any suitable corrosion inhibitor may be used. For example, the corrosion inhibitor may include yttrium, lanthanum, cerium, calcium, azole, or any combination thereof.

[0134] Non-limiting examples of suitable azoles include benzotriazole, 5-methylbenzotriazole, 2-aminothiazole, and their salts.

[0135] Corrosion inhibitors(s) may, if present, be present in the electrodeposited coating composition in an amount of at least 0.001% by weight, for example, at least 5% by weight, based on the total weight of the electrodeposited coating composition. Corrosion inhibitors(s) may, if present, be present in the electrodeposited coating composition in an amount of 25% by weight or less, for example, 15% by weight or less, for example, 10% by weight or less, based on the total weight of the electrodeposited coating composition. Corrosion inhibitors(s) may, if present, be present in the electrodeposited coating composition in an amount of 0.001% to 25% by weight, for example, 0.001% to 15% by weight, for example, 0.001% to 10% by weight, for example, 5% to 25% by weight, for example, 5% to 15% by weight, for example, 5% to 10% by weight, based on the total weight of the electrodeposited coating composition.

[0136] Alternatively, the electrodeposited coating composition may be substantially, essentially, or completely free of corrosion inhibitors.

[0137] According to this disclosure, the electrodepositable coating composition may contain other optional components, including a variety of additives such as fillers, plasticizers, antioxidants, biocides, ultraviolet absorbers and stabilizers, hindered amine light stabilizers, defoamers, bactericides, dispersants, flow control agents, surfactants, wetting agents, or combinations thereof. Alternatively, the electrodepositable coating composition may not contain any optional components at all, i.e., the optional components are not present in the electrodepositable coating composition. The above-mentioned other additives may be present in the electrodepositable coating composition in amounts from 0.01% to 3% by weight, cumulatively or individually, based on the total weight of the resin solids content of the electrodepositable coating composition.

[0138] According to this disclosure, the electrodepositable coating composition may contain water and / or one or more organic solvents. Water may be present in an amount of 40% to 90% by weight, for example, 50% to 75% by weight, based on the total weight of the electrodepositable coating composition. Examples of suitable organic solvents include oxygenated organic solvents, such as monoalkyl ethers of ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol containing 1 to 10 carbon atoms in the alkyl group, for example, monoethyl and monobutyl ethers of these glycols. Examples of other at least partially water-miscible solvents include alcohols such as ethanol, isopropanol, butanol, and diacetone alcohol. When used, the organic solvent may typically be present in an amount of less than 10% by weight, for example, less than 5% by weight, based on the total weight of the electrodepositable coating composition. The electrodepositable coating composition may be provided in particular in the form of a dispersion, such as an aqueous dispersion.

[0139] According to this disclosure, the total solids content of the electrodepositable coating composition may be at least 1% by weight, for example, at least 5% by weight, and may be 50% by weight or less, for example, 40% by weight or less, for example, 20% by weight or less, based on the total weight of the electrodepositable coating composition. The total solids content of the electrodepositable coating composition may be 1% to 50% by weight, for example, 5% to 40% by weight, for example, 5% to 20% by weight, based on the total weight of the electrodepositable coating composition. As used herein, "total solids" refers to the non-volatile components of the electrodepositable coating composition, i.e., materials that do not volatilize when heated at 110°C for 15 minutes.

[0140] The electrodepositable coating composition can be electrophoretically applied to an electrically conductive substrate and at least partially cured using application conditions, time, and temperature known to those skilled in the art.

[0141] The cationic electrodeposition coating composition of this disclosure can be deposited on an electrically conductive substrate by contacting it with an electrically conductive cathode and an electrically conductive anode, with the coated surface becoming the cathode. After contact with the composition, when a sufficient voltage is applied between the electrodes, an adhesive coating of the coating composition can be deposited on the cathode.

[0142] The anionic electrodeposition coating composition of this disclosure can be deposited on an electrically conductive substrate by contacting it with an electrically conductive cathode and an electrically conductive anode, with the coated surface becoming the anode. After contact with the composition, if a sufficient voltage is applied between the electrodes, an adhesive coating of the coating composition can be deposited on the anode.

[0143] The applied voltage in the electrophoretic application examples of the electrodepositable coating compositions of this disclosure can vary, for example, in the range of 1 volt to several thousand volts, for example, between 50 volts and 500 volts. The current density is, for example, between 0.5 amperes and 15 amperes per square foot, and tends to decrease during electrodeposition, which indicates the formation of an insulating coating.

[0144] Press spray composition As previously mentioned, a system for processing a substrate may include a pre-spray composition. The pre-spray composition essentially consists of, or may consist of, a surfactant, a binder, and optionally water.

[0145] The surfactant may be any surfactant disclosed herein above. The surfactant may be present in the pre-spray composition in an amount of at least 50 ppm, e.g., at least 100 ppm, e.g., at least 200 ppm, e.g., at least 500 ppm, based on the total weight of the pre-spray composition. The surfactant may be present in the pre-spray composition in an amount of 20,000 ppm or less, e.g., 10,000 ppm or less, e.g., 7,500 ppm or less, e.g., 5,000 ppm or less, based on the total weight of the pre-spray composition. The surfactant may be present in the pre-spray composition in an amount of 50 ppm to 20,000 ppm, e.g., 100 ppm to 10,000 ppm, e.g., 200 ppm to 7,500 ppm, e.g., 500 ppm to 5,000 ppm, based on the total weight of the pre-spray composition.

[0146] The builder may suppress or reduce the occurrence of flash rust. The builder may include any of the builders disclosed herein above. The builder may optionally include sodium tripolyphosphate.

[0147] The builder may be present in the press spray composition in an amount of at least 5 ppm, for example, at least 10 ppm, for example, at least 50 ppm, based on the total weight of the press spray composition. The builder may be present in the press spray composition in an amount of 2,000 ppm or less, for example, 1,500 ppm or less, for example, 1,000 ppm or less, based on the total weight of the press spray composition. The builder may be present in the press spray composition in an amount of 5 ppm to 5,000 ppm, for example, 20 ppm to 2,000 ppm, for example, 50 ppm to 1,000 ppm, based on the total weight of the press spray composition.

[0148] The pre-spray composition may have a pH of at least 1, for example, at least 2, for example, at least 2.5, for example, at least 5. The pre-spray composition may have a pH of 8.5 or less, for example, 8 or less, for example, 7.5 or less. The pre-spray composition may have a pH of 1 to 8.5, for example, 2 to 8, for example, 2.5 to 7.5, for example, 5 to 7.5.

[0149] The pre-spray composition may be substantially, essentially, or completely free of phosphates and / or chromium.

[0150] The press spray composition may include an aqueous medium, an organic medium, or a combination thereof. Examples of organic mediums include, but are not limited to, glycol ethers and / or high-flash hydrocarbon solvents.

[0151] In the example, the solution or dispersion of the press-spray composition may be applied to or in contact with the substrate surface by conventional means known in the art. For example, the solution or dispersion may be brought into contact with the substrate using a variety of known techniques, such as immersion or penetration, spraying, intermittent spraying, spraying followed by immersion, spraying followed by immersion, brushing, or roll coating. When the solution or dispersion is applied to a metal substrate, the temperature may be in the range of 10°C to 90°C, for example, 25°C to 75°C. For example, this process can be carried out at ambient temperature or room temperature. The contact time is often between 5 seconds and 5 minutes, for example, 10 seconds to 2 minutes.

[0152] method This disclosure is further directed to a method for coating a substrate, comprising applying one of the cleaner coater compositions disclosed herein to at least a portion of the surface of the substrate.

[0153] This disclosure is further directed to a method for treating a substrate, which includes applying either the cleaner coater composition or the electrodepositable coating composition disclosed herein.

[0154] The substrate may come into contact with the cleaner coater composition before coming into contact with the electrodepositable coating composition.

[0155] The method may optionally further include a rinsing step between the application of the cleaner coater composition and the application of the electrodepositable coating composition. Alternatively, the method may exclude the rinsing step between the application of the cleaner coater composition and the application of the electrodepositable coating composition.

[0156] The method for treating the substrate may further optionally include treating the substrate with any of the press-spray compositions disclosed herein. This method may omit a rinsing step between the application of the press-spray composition and the application of the cleaner coater composition.

[0157] The substrate may come into contact with the press spray composition before coming into contact with the cleaner coater composition. The substrate may come into contact with the cleaner coater composition before coming into contact with the electrodeposited coating composition.

[0158] A cleaner coater composition solution or dispersion can be spontaneously applied to or brought into contact with a substrate surface. For example, the solution or dispersion can be brought into contact with the substrate using various known techniques, such as immersion or penetration, spraying, intermittent spraying, spraying followed by immersion, spraying followed by immersion, brushing, or roll coating. When applied to a metal substrate, the temperature of the solution or dispersion may be in the range of 20°C to 50°C, for example, 25°C to 40°C. For example, this process may be carried out at ambient temperature or room temperature. The contact time is often 15 seconds to 5 minutes, for example, 30 seconds to 4 minutes, for example, 1 minute to 3 minutes. As used herein, the terms “spontaneous” or “autonomously,” when used in relation to a cleaner coater composition, refer to a cleaner coater composition that can react with the substrate surface, chemically modify the substrate surface, and bond to the substrate surface in order to form a protective layer without the presence of an externally applied voltage.

[0159] After the cleaner coater composition is applied to at least a portion of the substrate surface, the substrate may optionally be rinsed with an aqueous solution of tap water, deionized water, and / or a rinse agent to remove any residue. The damp substrate surface may be treated with one of the electrodepositable coating compositions described below, or before further treatment of the substrate surface, it may be dried, for example, by air-drying using an air knife, by exposing the substrate to a high temperature for a short period of time, for example 15°C to 100°C, for example 20°C to 90°C to evaporate moisture, by heating at 70°C for 10 minutes in a heater assembly using infrared heating, for example, or by passing it between squeegee rolls.

[0160] After applying the electrodepositable coating composition, the substrate may be heated to a temperature and time sufficient to at least partially cure the electrodeposited coating on the substrate. As used herein, the term “at least partially cured” means subjecting the coating composition to curing conditions such that some of the reactive groups of the components of the coating composition cure or crosslink to form a coating. Generally, the substrate may be heated to a temperature in the range of 250°F to 450°F (121.1°C to 232.2°C), for example, 275°F to 400°F (135°C to 204.4°C), for example, 300°F to 360°F (149°C to 180°C). For the purposes of this disclosure, all that is required is sufficient time to cure the coating on the substrate. The curing time can be, for example, in the range of 10 to 60 minutes, for example, 20 to 40 minutes. The thickness of the resulting cured electrodeposited coating is not limited and can optionally be in the range of 15 to 50 microns.

[0161] This method may optionally exclude the application of additional cleaning compositions that are not among the compositions disclosed herein.

[0162] Base material This disclosure is also directed to substrates treated with one of the cleaner coater compositions, systems, and / or methods disclosed herein.

[0163] Suitable substrates that may be used include metal substrates, metal alloy substrates, and / or metallized substrates such as nickel-plated plastics. Metals or metal alloys may include, or may be, steel, aluminum, zinc, nickel, and / or magnesium. For example, steel substrates may be cold-rolled steel, hot-rolled steel, electro-galvanized steel, and / or hot-dip galvanized steel. Aluminum alloys of the 1XXX, 2XXX, 3XXX, 4XXX, 5XXX, 6XXX, or 7XXX series, as well as clad aluminum alloys, may also be used as substrates. Aluminum alloys may contain, for example, 0.01 wt% to 10 wt% copper. Processed aluminum alloys may also include castings of 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 from the AZXX (including Eform Plus), AMXX, EVXX, ZEXX, ZCXX, HKXX, HZXX, QEXX, QHXX, WEXX, ZEK100, or Elektron 21 series may also be used as substrates. Substrates used may also include titanium and / or titanium alloys, zinc and / or zinc alloys, and / or nickel and / or nickel alloys. Suitable substrates used in this disclosure often include those used in assemblies of vehicle bodies (e.g., without limitation, doors, body panels, trunk deck lids, roof panels, hoods, roofs and stringers, rivets, landing gear components, and / or skins used in aircraft), vehicle frames, vehicle components, motorcycles, wheels, industrial structures, and components of appliances such as washing machines, dryers, refrigerators, stoves, and dishwashers, personal electronics, agricultural machinery, gardening equipment, metal fences, guardrails, air conditioning units, heat pump units, heat exchangers, lawn furniture, and other articles. As used herein, “vehicle” or its variations include, but are not limited to, civilian aircraft, commercial aircraft, military aircraft, and / or land vehicles such as automobiles, motorcycles, trucks, and / or bicycles, including electric bicycles.The metal substrate may also take the form of, for example, a metal sheet or a fabricated part.

[0164] In the example, the base material may be a polymetallic article. As used herein, the term “polymetallic article” means (1) an article having at least one surface made of a first metal and at least one surface made of a second metal different from the first metal, (2) a first product having at least one surface made of a first metal and a second product having at least one surface made of a second metal different from the first metal, or (3) both (1) and (2).

[0165] In the example, the base material may include a battery or battery components. Battery components include, but are not limited to, battery cells, battery shells, battery modules, battery packs, battery boxes, battery cell casings, pack shells, battery covers and trays, thermal management systems, battery housings, module housings, module racking, battery side plates, battery cell housings, cooling modules, cooling tubes, cooling fins, cooling plates, busbars, battery frames, electrical connections, metal wires, or copper or aluminum conductors or cables. The battery may be, for example, a battery for an electric vehicle, and the battery components may be, for example, battery components for an electric vehicle.

[0166] In the example, the substrate may include three-dimensional components formed by additive manufacturing processes such as selective laser melting, electron beam melting, directed energy deposition, binder jetting, and metal extrusion. In the example, the three-dimensional components may be metal and / or resin components.

[0167] The substrate may include a coating on at least a portion of its surface. The coating may be formed from any of the cleaner coater compositions disclosed herein. The coating may be formed from any of the electrodepositable coating compositions disclosed herein. The substrate may include a first coating on at least a portion of the substrate surface formed from any one of the cleaner coater compositions disclosed herein, and a second coating on at least a portion of the substrate surface formed from any one of the electrodepositable coating compositions disclosed herein.

[0168] Additional coating layers may be added to the substrate, including suitable additional coating layers known in the art, each independently in the form of aqueous, solvent-based, solid particulate (i.e., powder coating composition), or powder slurry. Each additional coating layer may be cured independently or optionally applied "wet-on-wet" and cured simultaneously. As used herein, "wet-on-wet" refers to a process in which a coating, such as a clear coat, is applied on top of a substantially uncured different coating, such as a color coat, and both coatings are cured simultaneously.

[0169] The mass ratio of Group IVB metals to electropositive metals in a coating formed from one of the cleaner coater compositions disclosed herein may be at least 1:10, for example at least 3:22, or for example at least 1:6. The mass ratio of Group IVB metals to electropositive metals in a coating formed from one of the cleaner coater compositions disclosed herein may be 2:1 or less, for example at least 1:1, or for example at least 1:2. The mass ratio of Group IVB metals to electropositive metals in a coating formed from one of the cleaner coater compositions disclosed herein may be 1:10 to 1:2, for example at least 3:22 to 1:1, or for example at least 1:6 to 1:2.

[0170] The coating formed from the cleaner coater composition was measured by ICP-OES to be 50 mg / m². 2Less than, for example, 3 mg / m² 2 ~20mg / m 2 It may contain amounts of IVB group metals.

[0171] The coating formed from the cleaner coater composition has a density of at least 5 mg / m², as measured by ICP-OES. 2 It may contain an amount of electronegativist metal.

[0172] Surprisingly, it has been found that substrates treated with one of the cleaner coater compositions disclosed herein exhibit a lower IVB group coating weight and improved corrosion resistance compared to substrates treated with conventional cleaning compositions and conventional pretreatment compositions. Thus, the cleaner coater compositions disclosed herein surprisingly offer improved corrosion resistance with fewer processing steps. Furthermore, it has been surprisingly found that substrates treated with one of the press spray compositions disclosed herein and one of the cleaner coater compositions disclosed herein can eliminate the rinsing step between the application of the compositions while maintaining corrosion resistance, compared to substrates treated with conventional cleaning compositions and conventional pretreatment compositions.

[0173] manner 1. A cleaner coater composition, Based on the total weight of the cleaner coater composition, the amount of IVB group metals is 50 ppm to 8,000 ppm, Electropositive metals such as copper, Builders containing phosphonates and / or sugar alcohols, Based on the total weight of the cleaner coater composition, the amount of surfactant is 50 ppm to 20,000 ppm, A cleaner coater composition containing the following: 2. A cleaner coater composition according to Embodiment 1, wherein the Group IVB metal comprises zirconium, titanium, or a combination thereof, and the Group IVB metal is optionally provided by zirconic acid hexafluoride, titanic acid fluoride, any of the aforementioned salts, or any of the aforementioned combinations. 3. Group IVB metals, (a) Based on the total weight of the cleaner coater composition, at least 100 ppm, for example at least 150 ppm, for example at least 200 ppm, for example at least 500 ppm, for example at least 600 ppm, for example at least 700 ppm, for example at least 800 ppm, for example at least 900 ppm, (b) Based on the total weight of the cleaner coater composition, 6,000 ppm or less, e.g., 5,000 ppm or less, e.g., 4,000 ppm or less, e.g., 3,000 ppm or less, e.g., 2,000 ppm or less, e.g., 1,500 ppm or less, and / or (c) A cleaner coater composition according to Embodiment 1 or Embodiment 2, comprising, based on the total weight of the cleaner coater composition, in an amount of 100 ppm to 6,000 ppm, for example 150 ppm to 4,000 ppm, for example 200 ppm to 2,000 ppm, for example 500 ppm to 5,000 ppm, for example 500 ppm to 1,500 ppm, for example 600 ppm to 4,000 ppm, for example 700 ppm to 3,000 ppm, for example 800 ppm to 2,000 ppm, for example 900 ppm to 1,500 ppm. 4. The electronegative metal, (a) Based on the total weight of the cleaner coater composition, at least 2 ppm, for example at least 10 ppm, for example at least 20 ppm, (b) Based on the total weight of the cleaner coater composition, 200 ppm or less, e.g., 100 ppm or less, e.g., 75 ppm or less, e.g., 40 ppm or less, and / or (c) A cleaner coater composition of any prior embodiment, comprising 2 ppm to 200 ppm, for example 2 ppm to 75 ppm, for example 10 ppm to 200 ppm, or for example 20 ppm to 40 ppm, based on the total weight of the cleaner coater composition. 5. A cleaner coater composition of any of the preceding embodiments, wherein the phosphonate comprises a monophosphonate, a diphosphonate such as etidronic acid, and / or a polyphosphonate, and / or the sugar alcohol comprises sorbitol. 6. A system of any prior embodiment in which the builder includes a flash rust inhibitor. 7. Builder, (a) Based on the total weight of the cleaner coater composition, at least 10 ppm, for example, at least 30 ppm, for example, at least 50 ppm, (b) Based on the total weight of the cleaner coater composition, 2,500 ppm or less, e.g., 2,000 ppm or less, e.g., 1,500 ppm or less, and / or (c) A cleaner coater composition of any prior embodiment, comprising 10 ppm to 2,500 ppm, for example 30 ppm to 2,000 ppm, or for example 50 ppm to 1,500 ppm, based on the total weight of the cleaner coater composition. 8. A system of any prior embodiment in which the surfactant comprises a cationic surfactant, an anionic surfactant, a nonionic surfactant, and / or an amphoteric surfactant. 9. Surfactants, (a) Based on the total weight of the cleaner coater composition, at least 100 ppm, for example, at least 200 ppm, for example, at least 500 ppm, (b) Based on the total weight of the cleaner coater composition, 10,000 ppm or less, e.g., 7,500 ppm or less, e.g., 5,000 ppm or less, and / or (c) A cleaner coater composition of any prior embodiment, comprising in an amount of 100 ppm to 10,000 ppm, for example 200 ppm to 7,500 ppm, or for example 500 ppm to 5,000 ppm, based on the total weight of the cleaner coater composition. 10. A cleaner coater composition of any of the preceding embodiments, wherein the cleaner coater composition is substantially, essentially, or completely free of phosphonates and / or sodium nitrobenzenesulfonate. 11. (a) Aqueous media and (b) Total fluoride, which can be optionally selected (i) Based on the total weight of the cleaner coater composition, at least 60 ppm, for example at least 125 ppm, for example at least 200 ppm, for example at least 250 ppm, (ii) Based on the total weight of the cleaner coater composition, 10,000 ppm or less, e.g., 7,500 ppm or less, e.g., 5,000 ppm or less, e.g., 3,000 ppm or less, e.g., 2,500 ppm or less, and / or (iii) Total fluoride in an amount of 60 ppm to 10,000 ppm, e.g., 125 ppm to 7,500 ppm, e.g., 200 ppm to 5,000 ppm, e.g., 250 ppm to 2,500 ppm, and / or based on the total weight of the cleaner coater composition. (c) Free fluoride, which can be optionally selected (i) Based on the total weight of the cleaner coater composition, at least 25 ppm, for example at least 35 ppm, for example at least 50 ppm, (ii) Based on the total weight of the cleaner coater composition, 750 ppm or less, for example 600 ppm or less, for example 500 ppm or less, and / or (iii) A cleaner coater composition of any prior embodiment further comprising, based on the total weight of the cleaner coater composition, an amount of free fluoride ranging from 25 ppm to 750 ppm, for example, 35 ppm to 600 ppm, for example, 50 ppm to 500 ppm. 12. A system for processing a substrate, A cleaner coater composition of any of the prior embodiments, An electrodepositable coating composition for at least partially coating a portion of the surface of a substrate treated with a cleaner coater composition, A system that includes this. 13. A system for processing a substrate, A cleaner coater composition comprising 50 ppm to 8,000 ppm of a group IVB metal, an electropositive metal such as copper, and 50 ppm to 20,000 ppm of a surfactant based on the total weight of the cleaner coater composition, An electrodepositable coating composition for at least partially coating a portion of the surface of a substrate treated with a cleaner coater composition, A system that includes this. 14. A system according to embodiment 12 or embodiment 13, wherein the electrodepositable coating composition comprises an active hydrogen-containing ionic base-containing film-forming polymer, a curing agent, and an electrodepositable binder containing a plate-like pigment. 15. The system of embodiment 14, wherein the electrodepositable coating composition contains plate-like pigments in a pigment-to-binder ratio of at least 0.4:1, for example at least 0.5:1, for example at least 0.6:1, for example at least 0.75:1, for example at least 1:1, for example at least 1.25:1, for example at least 1.5:1. 16. The plate-shaped pigment is at least, (a) When measured by dynamic light scattering, at least 50 nm, e.g., at least 0.2 microns, e.g., at least 0.4 microns, e.g., at least 0.6 microns, e.g., at least 1 micron, e.g., at least 2 microns, e.g., at least 3 microns, e.g., at least 4 microns, e.g., at least 5 microns, (b) When measured by dynamic light scattering, the size is 25 microns or less, e.g., 15 microns or less, e.g., 10 microns or less, e.g., 5 microns or less, e.g., 3.5 microns or less, e.g., 2.5 microns or less, e.g., 1.9 microns or less, e.g., 1.5 microns or less, e.g., 1 micron or less, and / or (c) A system of embodiment 14 or embodiment 15 having an average spherical equivalent diameter measured by dynamic light scattering of 50 nm to 25 microns, e.g., 0.2 microns to 15 microns, e.g., 0.4 microns to 10 microns, e.g., 0.6 microns to 5 microns, e.g., 1 micron to 3.5 microns, e.g., 2 microns to 15 microns, e.g., 3 microns to 10 microns, e.g., 4 microns to 25 microns, e.g., 5 microns to 25 microns, e.g., 50 nm to 2.5 microns, e.g., 0.2 microns to 1.9 microns, e.g., 0.4 microns to 1.5 microns, e.g., 50 nm to 1 micron. 17. A system according to any of embodiments 14 to 16, wherein the plate-like pigment comprises a phyllosilicate pigment containing mica, chlorite, serpentine, talc, clay such as kaolin clay, or a combination thereof. 18. A system according to any one of embodiments 12 to 17, wherein the electrodepositable coating composition comprises a film-forming polymer including blocked polyisocyanate, aminoplast, phenolplast, or a combination thereof. 19. A system according to any of embodiments 12 to 18, wherein the system excludes a separate cleaning step. 20. A system according to any of embodiments 12 to 19, further comprising a press spray composition, wherein the press spray composition contains a surfactant in an amount of 50 ppm to 20,000 ppm based on its total weight. 21. A system according to embodiment 20, wherein the surfactant includes a cationic surfactant, an anionic surfactant, a nonionic surfactant, an amphoteric surfactant, or a combination thereof. 22. The press spray composition is (a) Based on the total weight of the press spray composition, at least 50 ppm, for example at least 100 ppm, for example at least 200 ppm, for example at least 500 ppm, (b) Based on the total weight of the press spray composition, 20,000 ppm or less, e.g., 10,000 ppm or less, e.g., 7,500 ppm or less, e.g., 5,000 ppm or less, and / or (c) A system according to embodiment 20 or 21, comprising the surfactant in an amount of 50 ppm to 20,000 ppm, for example 100 ppm to 10,000 ppm, for example 200 ppm to 7,500 ppm, or for example 500 ppm to 5,000 ppm, based on the total weight of the press spray composition. 23. A system according to any of embodiments 20 to 22, wherein the press spray composition further comprises a builder. 24. The system of embodiment 23, wherein the builder comprises a monophosphate, a diphosphonate such as etidronic acid, and / or a polyphosphonate, and / or the builder comprises a sugar alcohol such as sorbitol. 25. The press spray composition is (a) Based on the total weight of the press spray composition, at least 5 ppm, for example at least 10 ppm, for example at least 50 ppm, (b) Based on the total weight of the press spray composition, 2,000 ppm or less, e.g., 1,500 ppm or less, e.g., 1,000 ppm or less, and / or (c) A system of embodiment 23 or embodiment 24, comprising a builder in an amount of 5 ppm to 5,000 ppm, for example 20 ppm to 2,000 ppm, or for example 50 ppm to 1,000 ppm, based on the total weight of the press spray composition. 26. A system according to any of embodiments 20 to 22, wherein the press-spray composition substantially, essentially, or completely lacks a builder. 27. A system according to any of embodiments 20 to 26, wherein the system excludes a rinsing step. 28. A method for coating a substrate, comprising applying any composition according to embodiments 1 to 11 to at least a portion of the surface of the substrate. 29. A method for coating a substrate, Applying a cleaner coater composition according to any of embodiments 12 to 27 to at least a portion of the surface of the substrate, A method comprising applying an electrodepositable coating composition according to any of embodiments 12 to 27 to at least a portion of the surface of a substrate coated with a cleaner coater composition. 30. The method according to embodiment 29, wherein the method excludes a separate cleaning step. 31. A method of any of embodiments 28 to 30, further comprising applying a press spray composition of any of embodiments 20 to 27 to the surface of a substrate. 32. The method according to embodiment 31, wherein the press spray is applied before the cleaner coater composition. 33. A method according to embodiment 31 or embodiment 32, wherein the method excludes a rinsing step. 34. A substrate treated with any of the cleaner coater compositions of embodiments 1 to 11. 35. A substrate processed by any system of any of embodiments 12 to 27. 36. A substrate treated by any of the methods described in embodiments 28 to 33. 37. A substrate according to any of embodiments 34 to 36, comprising a coating formed by applying a cleaner coater composition to at least a portion of the surface of the substrate. 38. A substrate according to embodiment 37, wherein the coating comprises an IVB group metal and / or an electronegative metal. 39. The coating is (a) Group IVB metals and electronegative metals, (i) at least 1:10, for example at least 3:22, for example at least 1:6, (ii) 2:1 or less, e.g., 1:1 or less, e.g., 1:2 or less, and / or (iii) A weight ratio of 1:10 to 2:1, for example 3:22 to 1:1, for example 1:6 to 1:2, with a group IVB metal and the electropositive metal, (b) When measured by ICP-OES, it was 50 mg / m² 2 Less than a certain amount of Group IVB metals, and / or (c) When measured by ICP-OES, it is at least 5 mg / m² 2 A substrate according to any of embodiments 34 to 38, comprising an amount of an electropositive metal. 40. A substrate according to any of embodiments 34 to 39, further comprising a second coating formed on at least a portion of a coating formed from a coating composition by applying an electrodepositable coating composition thereon. 41. A substrate according to any of embodiments 34 to 40, wherein the substrate includes an article, a part, or a combination thereof. 42. A substrate according to embodiment 41, wherein the article includes a vehicle, equipment, personal electronic device, circuit board, battery cell, polymetallic substrate, or a combination thereof. 43. A substrate according to embodiment 41, wherein the components include vehicle parts. 44. A substrate according to embodiment 42, wherein the vehicle includes a land vehicle or an aircraft. 45. A substrate according to any of embodiments 37 to 44, further comprising a second coating formed by applying an electrodepositable coating composition to at least a portion of the surface of a substrate including a first coating. 46. ​​Use for providing a coating formed from any cleaner coater composition of any of embodiments 1 to 11, wherein the coating is (a) Group IVB metals and electronegative metals, (i) at least 1:10, for example at least 3:22, for example at least 1:6, (ii) 2:1 or less, e.g., 1:1 or less, e.g., 1:2 or less, and / or (iii) Group IVB metals and electropositive metals in weight ratios of 1:10 to 2:1, for example 3:22 to 1:1, for example 1:6 to 1:2, (b) When measured by ICP-OES, it was 50 mg / m² 2 Less than a certain amount of Group IVB metals, and / or (c) When measured by ICP-OES, it is at least 5 mg / m² 2 Uses an amount of electronegative metal, including. 47. Use for providing a coating formed from any cleaner coater composition of any of embodiments 12 to 25, wherein the coating is (a) Group IVB metals and the aforementioned electropositive metals, (i) at least 1:10, for example at least 3:22, for example at least 1:6, (ii) 2:1 or less, e.g., 1:1 or less, e.g., 1:2 or less, and / or (iii) Group IVB metals and electropositive metals in weight ratios of 1:10 to 2:1, for example 3:22 to 1:1, for example 1:6 to 1:2, (b) When measured by ICP-OES, it was 50 mg / m² 2 Less than a certain amount of Group IVB metals, and / or (c) When measured by ICP-OES, it is at least 5 mg / m² 2 Uses an amount of electronegative metal, including. 48. A substrate having a first coating on at least a portion of its surface, wherein the coating is (a) Group IVB metals and electronegative metals, (i) at least 1:10, for example at least 3:22, for example at least 1:6, (ii) 2:1 or less, e.g., 1:1 or less, e.g., 1:2 or less, and / or (iii) Group IVB metals and electropositive metals in weight ratios of 1:10 to 2:1, for example 3:22 to 1:1, for example 1:6 to 1:2, (b) When measured by ICP-OES, it was 50 mg / m² 2 Less than a certain amount of Group IVB metals, and / or (c) When measured by ICP-OES, it is at least 5 mg / m² 2 A substrate containing an amount of an electropositive metal.

[0174] While aspects of this disclosure are described in detail, it will be understood by those skilled in the art that, in light of the overall teachings of this disclosure, various modifications and alternatives to those details can be developed. Accordingly, the specific configurations disclosed are illustrative only and are not intended to be limitations on the scope of this disclosure that would give the entirety of the appended claims or any and all equivalents thereof. [Examples]

[0175] Preparation of composition Cleaners, pretreatment agents, and cleaner coater compositions were prepared using the additives and surfactants described herein.

[0176] Preparation of alkaline cleaners: Alkaline cleaner solution (C1) was prepared in a rectangular stainless steel tank equipped with a spray nozzle using Chemkleen Surface Prep 1R (CKSP1R) (alkaline cleaner) and Chemkleen 185A (blended surfactant additive), both available from PPG Industries, Inc.

[0177] Preparation of the press spray composition: Press-spray composition (PS): A rectangular stainless steel tank with a total capacity of 37 gallons, equipped with a spray nozzle, was filled with 10 gallons of deionized water. Chemkleen 185A surfactant (38 mL), etidronic acid (2.88 g), 85% phosphoric acid (3 g), and sodium tripolyphosphate (25 g) were added to this.

[0178] Preparation of pretreatment: The pretreatment composition (PT1) was prepared by preparing Zircobond 1.5 (available from PPG Industries, Inc.) according to the manufacturer's instructions.

[0179] Preparation of the cleaner coater: Cleaner Coater 1 (C-C1): 18.85 liters of deionized water were added to a clean 5-gallon plastic bucket. Zirconate fluoride (96.6 g), etidronic acid (4.8 g), 2% copper(II) nitrate solution (25 g), and Chemkleen 185A (19 mL) were added. Etidronic acid (hydroxyethylidene (1,1-diphosphonic acid)) was used as a 60 wt% aqueous solution, available from Italmatch as Dequest 2010.

[0180] Cleaner Coater 2 (C-C2): A rectangular stainless steel tank with a total capacity of 37 gallons, equipped with a spray nozzle, was filled with 10 gallons of deionized water. To this, zirconate fluoride (193.2 g), etidronic acid (9.6 g), 2% copper from copper(II) nitrate solution (10 g), and Chemkleen 185A surfactant (38 mL) were added.

[0181] The C-C1 mixture was circulated and maintained at 120°F (50°C) using an immersion heater (Polyscience Sous Vide Professional, Model #7306AC1B5, available from Polyscience, Neils, Illinois), and the panel was set to high agitation mode during immersion to circulate and heat the composition contained therein.

[0182] After all components were added to C-C1 and C-C2, the 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, available from ThermoFisher Scientific) to immerse the ISE in solution and allow the measurement to reach equilibrium. The free fluoride was adjusted as needed using Chemfos AFL, a partially neutralized aqueous acidic ammonium fluoride solution available from PPG Industries, Inc.

[0183] pH was measured using a pH meter (Interface, DualStar pH / ISE Dual Channel Benchtop Meter, available from ThermoFisher Scientific (Wilham, Massachusetts, 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 to pH 4.5 as needed, while the pH of PS was adjusted to pH 7 as needed using Chemfil Buffer, available from PPG Industries, Inc.

[0184] The amount of copper in each bath was measured using a DR / 890 water quality analyzer (available from HACH, Loveland, Colorado, USA) with an indicator (CuVer2 copper reagent powder pillow, available from HACH). [Table 2]

[0185] Preparation of phosphate acrylic polyols: Component 1, listed in Table 2 below, was added to a flask set up for total reflux under nitrogen with stirring, and heated to 120°C. Components 9 and 10 (initiator packing 1) were added dropwise to the flask over 3 hours and 35 minutes. Five minutes after starting initiator packing 1, components 2-8 (monomer packing) were mixed in an addition funnel and added dropwise over 3.5 hours. After monomer packing was complete, the monomer-filled addition funnel was rinsed with packing 13. After both packings were complete, the reaction was held at 120°C for 1 hour. Then, components 11 and 12 (initiator packing 2) were added dropwise to the reaction flask through the addition funnel over 30 minutes. After initiator packing 2 was complete, the addition funnel was rinsed with component 14. The reaction was held at 120°C for 90 minutes, and then cooled to room temperature with stirring. The resulting phosphate acrylic polyol resin had a solids content of 56% by weight. [Table 3]

[0186] Preparation of Electrocoat A: Electrocoat A, a cationic amine functional epoxy / isocyanate crosslinked electrodeposition coating highly packed with plate-like pigments, was prepared. Components 1-4, shown in Table 3 below, were placed in a stainless steel beaker and mixed at high shear (2500 RPM with a 1.5-inch Cowles blade using a Fawcett Model 103A air motor) starting at 40°C for 5 minutes. The temperature was increased to over 60°C, and the mixture was maintained in the above mixture for 1 hour, after which the degree of dispersion was measured with a Hegman gauge. Dispersion was considered well-dispersed when the lowest reading of 5 was achieved.

[0187] In the dispersion step, a mixture of components 5 and 6 was added to the mixture. A temperature of less than 60°C was set, and the dispersion was mixed at 1500 RPM using a high-lift blade for 1 hour. After dispersion, the dispersion was cooled to ambient temperature, component 7 was added, and it was mixed for 1 hour to bring the final solids content of this dispersion paste to 40% by weight. Next, component 8 was added to the dispersion formulation and mixed at ambient temperature for 1 hour to complete the high-solids feed. To produce Electrocoat A, the high-solids feed was further diluted with component 9 until it had a solids content of 25% by weight. [Table 4]

[0188] Preparation of Electrocoat B A commercially available cationic electrodeposition coating composition, Electrocoat B (P:B ratio 0.15), was prepared according to the manufacturer's instructions.

[0189] Examples 1-4 The panels for Examples 1-4 were prepared using cold-rolled steel (CRS) and aluminum alloy 6111 (AA6111) supplied by ACT Test Panel (Hillsdale, Michigan).

[0190] Each panel was processed using processing methods A, B, C, or D, as shown in Tables 4, 5, 6, and 7, respectively.

[0191] For panels treated according to treatment method A, the panels were spray-cleaned with a cleaner (120°F) using a Vee-jet nozzle at 10-15 psi for 120 seconds, immersed in a deionized water bath (75°F) for 30 seconds to rinse with deionized water, and then rinsed with a deionized water spray using a Melnor Rear-Trigger7-Pattern nozzle (available at Home Depot) set to shower mode. Next, the panels were immersed in pre-treatment for 120 seconds (80°F), rinsed with a deionized water spray using a Melnor Rear-Trigger7-Pattern nozzle set to shower mode (75°F) for 30 seconds, and dried using a Hi-Velocity handheld blow dryer with hot air (140°F) for 120 seconds.

[0192] For panels treated according to treatment method B, the panels were spray-cleaned with a cleaner (120°F) at 10-15 psi for 120 seconds using a Vee-jet nozzle, then rinsed with deionized water spray for 30 seconds using a Melnor Rear-Trigger7-Pattern nozzle set to shower mode (75°F), and finally dried with hot air (140°F) for 120 seconds using an Oster® (model number 078302-300-000) Hi-Velocity handheld blow dryer on high setting.

[0193] For panels treated according to treatment method C, the panels were immersed and washed for 120 seconds (120°F), rinsed with deionized water spray for 30 seconds using a Melnor Rear-Trigger7-Pattern nozzle set to shower mode (75°F), and dried for 120 seconds with hot air (140°F) using a Hi-Velocity handheld blow dryer.

[0194] For panels treated according to treatment method D, the panels were spray-cleaned using a Vee-jet nozzle with a pre-spray (120°F) at 10-15 psi for 120 seconds. The panels were then immersed in additional cleaner for 120 seconds (120°F), rinsed with deionized water spray for 30 seconds using a Melnor Rear-Trigger7-Pattern nozzle set to shower mode (75°F), and dried using a Hi-Velocity handheld blow dryer with hot air (140°F) for 120 seconds. [Table 5] [Table 6] [Table 7] [Table 8]

[0195] After completion of processing methods A, B, C, or D, the panel was coated with electrocoat A or electrocoat B (a cationic electrocoat with a ratio of 0.15 p:B).

[0196] Each test panel was immersed in electrocoat and electrodeposited using a DC-powered rectifier (Xantrax Model XFR600-2, Elkhart, Indiana, or Sorensen XZG300-5.6, Ameteck, Belwyn, Pennsylvania). The exact coating conditions and film build for each coating are listed in Table 8. After electrodeposition, each panel was rinsed with deionized water and baked in an electric oven (Despatch Model LFD-1-42) at 177°C. [Table 9]

[0197] Electrodeposited panels were scribed vertically to the metal substrate on one side of the panel. To evaluate corrosion resistance, panels were subjected to a CASS (copper-chloride-acetic acid accelerated spray) test for a minimum of 20 days, or GMW14872 for a minimum of 30 cycles (i.e., 30 days). At the end of the test, panels were evaluated by measuring paint peeling (creep) from the scribe and the maximum creep phenomenon (in millimeters) calculated for each panel. After exposure, corroded panels were dried under ambient conditions. Loose coating around the scribe was removed by applying and peeling Scotch filament tape (3M Industries Adhesives and Tapes Divisions, St. Paul, MN). Next, the width of the exposed metal area along the scribe was recorded at 5 to 12 locations, and the average was taken to evaluate the corrosion resistance of the panel. As used herein, scribe creep refers to the area of ​​paint loss around the scribe due to corrosion or peeling (e.g., from affected paint to affected paint). Panels under each condition were performed overlappingly, and the results were averaged.

[0198] As described below, non-electrodeposited panels were subjected to zirconium deposition analysis by handheld X-ray fluorescence (XRF) measured using an X-Met8000, Oxford Instruments. Operating parameters for zirconium and copper were 120-second timed assay, 40 kV, 9 μA, Kα, T(p) = 1.1 μs (reported as XRF peak area Zr net count). The peak area was calculated by adding the XRF counts in the region of interest (ROI) or peak of the target element and then subtracting the count from the untreated control panel.

[0199] Example 1 CRS and AA6111 panels were treated with different treatment baths and methods. The panels were then electrodeposited with Electrocoat B according to the parameters described above. The panels were scribed and subjected to corrosion tests as specified in Table 9. [Table 10]

[0200] Example 1 demonstrates that CRS and AA6111 substrates treated with C-C1 exhibit improved or equivalent corrosion resistance compared to substrates treated with C1+PT1, and substantially improved corrosion resistance compared to substrates treated with C1 alone. Furthermore, the C-C1 treatment exhibits good corrosion resistance when using treatment method C, which has fewer process steps than the C1+PT1 treatment using treatment method A.

[0201] Example 2 CRS and AA6111 panels were treated with different treatment baths and methods. The panels were then electrodeposited with Electrocoat A according to the parameters described above. The panels were scribed and subjected to corrosion tests as specified in Table 10. [Table 11]

[0202] Example 2 shows that a substrate treated with C-C2 exhibits superior corrosion resistance in CRS and AA6111 compared to a substrate treated with C1+PT1, and further exhibits superior corrosion resistance in CRS and AA6111 compared to substrates treated with C1 and Electrocoat A. Overall, the substrate treated with C-C2 exhibits good corrosion resistance with fewer process steps than the substrate treated with P-S+C-C1, and both the substrate treated with C-C2 and the substrate treated with P-S+C-C1 exhibit even fewer process steps than the substrate treated with C1+PT1.

[0203] Example 3 CRS and AA6111 panels were treated with different treatment baths and methods and coated with different electrocoats. The panels were scribed and subjected to corrosion tests as specified in Table 11. [Table 12]

[0204] Example 3 demonstrates that substrates treated with C-C2 and Electrocoat A exhibited improved corrosion resistance in CRS and AA6111 compared to substrates treated with C1+PT1 and Electrocoat B. Substrates treated with C-C2 and Electrocoat A had significantly better corrosion resistance in CRS and AA6111 than substrates treated with either C1 and Electrocoat A or Electrocoat B. Therefore, treating the substrate with C-C2 required fewer processing steps than treating the substrate with C1+PT1, while still achieving superior corrosion resistance.

[0205] Example 4 CRS panels were treated with different treatment baths and methods, and exposed to 25 mL of 6N hydrochloric acid for 5 minutes to dissolve the pretreatment layer. Each etching agent solution was submitted to ICP-OES, and the concentrations of Cu and Zr were measured. These were converted to coating weight (milligrams per square meter) for each condition. Furthermore, CRS panels treated with different treatment baths and methods were analyzed by handheld XRF using the same parameters as above. The results are summarized in Table 12. [Table 13]

[0206] Example 4 demonstrates that the C-C1 and C-C2 treatments result in significantly lower Zr ICP coating weight and Zr XRF deposition compared to the comparative treatment C1+PT1. All treatments result in comparable Cu ICP coating weight but show slightly higher Cu XRF deposition. Substrates treated with C-C1 and C-C2 showed lower Zr ICP coating weight and Zr XRF deposition than substrates treated with C1+PT1, but exhibited improved or comparable corrosion resistance, as shown in Examples 1-3 above. Therefore, substrates treated with the cleaner coater compositions of this disclosure provide comparable or improved corrosion resistance with fewer steps and lower Zr deposition compared to substrates treated with cleaning compositions and pre-treatment compositions.

Claims

1. A cleaner coater composition, Based on the total weight of the cleaner coater composition, an amount of IVB group metals ranging from 50 ppm to 8,000 ppm is used. Electropositive metals, A builder containing phosphonates and / or sugar alcohols, Based on the total weight of the cleaner coater composition, a cleaner coater surfactant in an amount of 50 ppm to 20,000 ppm is added. A cleaner coater composition containing the following:

2. The cleaner coater composition according to claim 1, wherein the IVB group metal comprises zirconium, titanium, or a combination thereof, and the IVB group metal is optionally provided by zirconic acid hexafluoride, titanic acid fluoride, salts thereof, or a combination thereof.

3. The cleaner coater composition is (a) an amount of the electropositive metal, and / or based on the total weight of the cleaner coater composition, in an amount of 2 ppm to 200 ppm. (b) A cleaner coater surfactant in an amount of 100 ppm to 10,000 ppm based on the total weight of the cleaner coater composition, and / or (c) The cleaner coater composition according to claim 1 or claim 2, comprising the builder in an amount of 10 ppm to 2,500 ppm based on the total weight of the cleaner coater composition.

4. The cleaner coater composition according to any one of the prior claims, wherein the electropositive metal comprises copper.

5. The cleaner coater composition according to any one of the prior claims, wherein the phosphonate comprises a monophosphonate, a diphosphonate such as etidronic acid, and / or a polyphosphonate, and / or the sugar alcohol comprises sorbitol.

6. The cleaner coater composition according to any one of the prior claims, wherein the cleaner coater composition comprises a pH of 1.0 to 6.

0.

7. The cleaner coater composition according to any one of the prior claims, wherein the cleaner coater composition substantially does not contain a phosphonate and / or sodium nitrobenzenesulfonate.

8. The cleaner coater composition is (d) Based on the total weight of the cleaner coater composition, optionally 60 ppm to 10,000 ppm of total fluoride, and / or (e) The cleaner coater composition according to any one of the prior claims, comprising optionally 25 ppm to 750 ppm of free fluoride based on the total weight of the cleaner coater composition.

9. A system for processing a substrate, (a) The cleaner coater composition according to any one of the prior claims for treating at least a portion of the surface of the substrate, (b) an electrodepositable coating composition for at least partially coating the surface of the substrate treated with the cleaner coater composition, A system that includes this.

10. The system according to claim 9, wherein the electrodepositable coating composition comprises an ionic base-containing film-forming polymer and / or a curing agent, such as a blocked polyisocyanate, an aminoplast resin, a phenoplast resin, or a combination thereof.

11. The system according to claim 9 or 10, wherein the electrodepositable coating composition comprises a plate-like pigment present in a pigment-to-binder ratio of at least 0.4:

1.

12. A system for processing a substrate, A cleaner coater composition comprising, based on the total weight of the cleaner coater composition, an amount of IVB group metal in the range of 50 ppm to 8,000 ppm, an electropositive metal such as copper, and a surfactant in the range of 50 ppm to 20,000 ppm based on the total weight of the cleaner coater composition for treating at least a portion of the surface of the substrate, An electrodepositable coating composition for at least partially coating a portion of the surface of a substrate treated with the cleaner coater composition, comprising an electrodepositable binder containing an active hydrogen-containing ionic base-containing film-forming polymer, a curing agent, and a plate-like pigment, wherein the plate-like pigment is present in a pigment-to-binder ratio of at least 0.4:1, A system that includes this.

13. The system according to claim 11 or claim 12, wherein the plate-shaped pigment has an average spherical equivalent diameter of 50 nm to 25 microns.

14. The system according to any one of claims 9 to 13, further comprising a press spray composition, wherein the press spray composition comprises a builder and a surfactant in an amount of 50 ppm to 20,000 ppm based on the total weight of the press spray composition.

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

16. A method for processing a substrate, Applying the cleaner coater composition according to any one of claims 9 to 14 to at least a portion of the surface of the substrate, Applying the electrodepositable coating composition according to any one of claims 9 to 14 to at least a portion of the surface of the substrate to which the cleaner coater composition has been applied, Methods that include...

17. The method according to claim 16, wherein the method excludes a separate cleaning step.

18. The method according to claim 16 or claim 17, further comprising applying the press spray composition according to claim 14.

19. The method according to claim 18, wherein the rinsing step is excluded.

20. A substrate processed by the system described in any one of claims 9 to 14.

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

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

23. The aforementioned coating (a) The IVB group metal and the electronegativity metal, (i) at least 1:10, for example at least 3:22, for example at least 1:6, (ii) 2:1 or less, e.g., 1:1 or less, e.g., 1:2 or less, and / or (iii) The IVB group metal and the electronegativity metal in a weight ratio of 1:10 to 2:1, for example 3:22 to 1:1, for example 1:6 to 1:2 (b) When measured by ICP-OES, the result was 50 mg / m² ２ Less than an amount of the aforementioned IVB group metal, and / or, (c) At least 5 mg / m² as measured by ICP-OES ２ an amount of the aforementioned electronegativity metal, The substrate according to claim 22, including the above.

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