Cationic fire-resistant electrodepositable coating compositions

Abstract

The present disclosure is directed to a cationic fire-resistant electrodepositable coating composition comprising: a film-forming component; a hybrid organic-inorganic material; and an inorganic pigment. Also disclosed are methods of using such fire-resistant electrodepositable coating compositions to coat at least a portion of a substrate, and substrates coated by such methods.

Description

CATIONIC FIRE-RESISTANT ELECTRODEPOSIT ABLE COATING COMPOSITIONSFIELD OF THE DISCLOSURE

[0001] The present disclosure is directed to cationic fire-resistant electrodepositable coating compositions comprising a hybrid organic-inorganic material and an inorganic pigment.BACKGROUND INFORMATION

[0002] Fire resistant coatings have been used for a variety of structural applications to protect against both cellulosic and hydrocarbon fires. Such coatings offer protection by offering fire resistance to the coated substrate. Numerous substrates may benefit from being coated with such coatings, including structural building components used, for example, in commercial and transportation infrastructures like hotels, airports, concert halls or off-shore sites, chemical plants, oil rigs, and the like, that would be exposed to extreme heat in the case of fire. Energy storage devices, such as batteries, including lithium ion batteries, may also be exposed to such intense heat; many such devices are vulnerable to thermal runaways during which heat and gas are rapidly discharged and a fire hazard is created. Improved protective coatings, including those used for energy storage devices and the apparatus using such devices, are therefore desired.SUMMARY OF THE DISCLOSURE

[0003] Disclosed herein is a cationic fire-resistant electrodepositable coating composition comprising a film-forming component; a hybrid organic-inorganic material wherein the inorganic portion of the hybrid has an atom weight of 0.20 or greater based on total solids weight of the composition and has a P:B of less than 0.20:1; and an inorganic pigment, wherein the inorganic pigment has an atom wt% of 8 wt% or greater based on total solids weight of the composition. Also disclosed is a cationic fire-resistant electrodepositable coating composition comprising a film-forming component; a hybrid organic-inorganic material that is reactive with the film-forming component, wherein the inorganic portion of the hybrid has an atom wt% of 0.20 or greater based on total solids weight of the composition; and an inorganic pigment, wherein the inorganic pigment has an atom wt% of 8.0 wt% or greater based on total solids weight of the composition. Methods of using the coating compositions and substrates coated at least in part with a coating layer deposited from such compositions are also within the scope of the present disclosure.DETAILED DESCRIPTION OF THE DISCLOSURE

[0004] The present disclosure is generally directed to cationic fire-resistant electrodepositable coating compositions comprising a film-forming component, a hybrid organic-inorganic material, and an inorganic pigment. “Fire resistant”, “fire resistance” and like terms is used herein to describe the present compositions as well as coatings or coating layers deposited from any of the compositions.

[0005] ‘Fire resistant” means that a coating layer, when deposited onto a cold rolled steel panel and cured to a dry film thickness of 0.8 to 1 mil, does not ignite or sustain a flame when tested according to the DIRECT FIRE EXPOSURE TEST and has less than 7 mm of coating loss. The “DIRECT FIRE EXPOSURE TEST” is performed as described in the Examples section, below. A coating “ignites” if it continues burning once the flame is removed.

[0006] As used herein, “electrodepositable coating composition”, ecoat, ecoat composition, and like terms refer to a composition that is capable of being deposited onto an electrically conductive substrate under the influence of an electric potential applied between two electrodes immersed in the electrodepositable coating composition, where one of the electrodes is the substrate to be coated. A “cationic” ecoat refers to an electrodepositable coating composition capable of being deposited onto an electrically conductive substrate by a cationic electrodeposition process, wherein a coating deposited from the cationic electrodepositable coating composition deposits on the conductive substrate serving as the cathode during the electrodeposition process.

[0007] The coating compositions comprise a film-forming component. “Film-forming” means that the composition, upon drying and / or curing, can form a continuous film on a surface. This continuous film is often referred to herein as a coating or coating layer, all of which terms are used interchangeably herein. As used herein, “cure”, “cured”, “harden”, “drying” and like terms means that at least a portion of the film-forming components that can react or crosslink with themselves or each other do so, resulting in an at least partially cured coating layer. The film-forming component may include, for example, a film-forming resin and a crosslinker therefore. Any film-forming resin can be used according to the present disclosure, such as an organic film-forming resin. Such a resin can react with itself, that is, undergo a self-crosslinking reaction, or can react with a crosslinker to form a film. “Film-forming resin”, “film-former”, “resin”, “base” and like terms may be used interchangeably herein. “Crosslinker”, “curingagent”, “hardener”, and like terms may be used interchangeably herein. Such reactions may occur at ambient conditions or elevated temperature. “Ambient conditions” generally refers to room temperature (10°C to 32°C) and relative humidity of 20 to 80%, while “elevated temperature” generally refers to temperatures 33°C or higher.

[0008] Any suitable cationic salt group- containing film-forming resin or polymer (which terms are used interchangeably herein) can be used. “Cationic salt group-containing filmforming polymer” and like terms refer to polymers that include at least partially neutralized cationic salt groups that impart a positive charge, such as sulfonium groups, ammonium groups, or phosphonium groups. Examples of suitable polymers include alkyd polymers, acrylics, polyepoxides, polyamides, polyurethanes, polyureas, polyethers, and polyesters.

[0009] More specific examples of suitable cationic salt group containing film-forming polymers include poly epoxide- amine adducts, such as the adduct of a polyglycidyl ether of a polyphenol, such as Bisphenol A, and primary and / or secondary amines, such as those described in U.S. Patent No. 4,031,050 at col. 3, line 27 to col. 5, line 50, U.S. Patent No. 4,452,963 at col. 5, line 58 to col. 6, line 66, and U.S. Patent No. 6,017,432 at col. 2, line 66 to col. 6, line 26, these portions of which being incorporated herein by reference. A portion of the amine that is reacted with the polyepoxide may be a ketimine of a polyamine, as is described in U.S. Patent No. 4,104,147 at col. 6, line 23 to col. 7, line 23, the cited portion of which being incorporated herein by reference. Also suitable are ungelled polyepoxide-polyoxyalkylenepolyamine resins, such as are described in U.S. Patent No. 4,432,850 at col. 2, line 60 to col. 5, line 58, the cited portion of which being incorporated herein by reference. In addition, cationic acrylic resins, such as those described in U.S. Patent No. 3,455,806 at col. 2, line 18 to col. 3, line 61 and 3,928,157 at col. 2, line 29 to col. 3, line 21, these portions of both of which are incorporated herein by reference, may be used.

[0010] Besides amine salt group-containing resins, quaternary ammonium salt group- containing resins may also be employed as a cationic salt group-containing film-forming resin in the present disclosure. Examples are those resins formed from reacting an organic polyepoxide with a tertiary amine acid salt. Such resins are described in U.S. Patent No. 3,962,165 at col. 2, line 3 to col. 11, line 7; 3,975,346 at col. 1, line 62 to col. 17, line 25 and 4,001,156 at col. 1, line 37 to col. 16, line 7, these portions of which being incorporated herein by reference.

[0011] Examples of other suitable cationic resins include ternary sulfonium salt group- containing resins, such as those described in U.S. Patent No. 3,793,278 at col. 1, line 32 to col. 5, line 20, this portion of which being incorporated herein by reference. Also, cationic resins that cure via a transesterification mechanism can also be used, such as described in European Patent Application No. 12463B1 at pg. 2, line 1 to pg. 6, line 25, this portion of which being incorporated herein by reference.

[0012] Other suitable cationic salt group-containing film-forming polymers include those that may form photodegradation resistant electrodepositable coating compositions. Such polymers include the polymers comprising cationic amine salt groups that are derived from pendant and / or terminal amino groups that are disclosed in U.S. Patent Application Publication No. 2003 / 0054193 Al at paragraphs

[0064] to

[0088] , this portion of which being incorporated herein by reference. Also suitable are the active hydrogen-containing, cationic salt group- containing resins derived from a polyglycidyl ether of a polyhydric phenol, which are bonded to more than one aromatic group, and are described in U.S. Patent Application Publication No. 2003 / 0054193 Al at paragraphs

[0096] to

[0123] , this portion of which being incorporated herein by reference. Also suitable are polypropylene oxide diepeoxide resins, such as DER-732, commercially available from Palmer Holland.

[0013] The active hydrogen-containing, cationic salt group-containing film-forming polymer is made cationic and water dispersible by at least partial neutralization with a neutralizing acid. Suitable neutralizing acids include organic and inorganic acids. Non-limiting examples of suitable organic neutralizing acids include formic acid, acetic acid, methanesulfonic acid, and lactic acid. Non-limiting examples of suitable inorganic neutralizing acids include a sulfamic acid. By “sulfamic acid” is meant sulfamic acid itself or derivatives thereof such as those having the formula:H — N — S O H3 wherein R is hydrogen or an alkyl group having 1 to 4 carbon atoms. Mixtures of the above- mentioned acids also may be used according to the present disclosure.

[0014] The extent of neutralization of the cationic salt group-containing film-forming polymer may vary with the particular polymer involved. However, sufficient neutralizing acidshould be used to sufficiently neutralize the cationic salt group-containing film-forming polymer such that the cationic salt group-containing film-forming polymer may be dispersed in an aqueous dispersing medium. For example, the amount of neutralizing acid used may provide at least 20% of all of the total theoretical neutralization. Excess neutralizing acid may also be used beyond the amount required for 100% total theoretical neutralization. For example, the amount of neutralizing acid used to neutralize the cationic salt group-containing film-forming polymer may be ^0.1% based on the total amines in the active hydrogen-containing, cationic salt group- containing film-forming polymer. Alternatively, the amount of neutralizing acid used to neutralize the active hydrogen-containing, cationic salt group-containing film-forming polymer may be 100% based on the total amines in the active hydrogcn-containing, cationic salt group- containing film-forming polymer. The total amount of neutralizing acid used to neutralize the cationic salt group-containing film-forming polymer may be in a range of any combination of values, which were recited in the preceding sentences, inclusive of the recited values. For example, the total amount of neutralizing acid used to neutralize the active hydrogen-containing, cationic salt group-containing film-forming polymer may be 20%, 35%, 50%, 60%, or 80% based on the total amines in the cationic salt group-containing film-forming polymer. Other acidic additives may be incorporated into the fire-resistant electrodepositable compositions leading to an increase in the total theoretical neutralization relative to just amount added with the neutralizing acid. When these acidic additives are present in the composition, the total theoretical neutralization (%TN) may be 60% to 250% TN, such as 65% to 200% TN, such as 70% to 175% TN, such as 75% to 150% TN.100151 The film-forming resin may be present in the fire-resistant electrodepositable coating composition in an amount of 5 wt% or greater, such as 20 wt% or greater, such as 30 wt% or greater, and may be present in an amount of 100 wt% or lower, such as 60 wt% or lower, such as 50 wt% or lower, such as 40 wt% or lower, such as 20 wt% or lower, , such as in an amount 5 to 100 wt%, such as 10 to 60 wt%, such as 20 to 40 wt%, such as 5 to 30 wt%, such as 5 to 20 wt%, such as 5 to 10 wt%, such as 20 to 100 wt%, such as 20 to 60 wt%, such as 20 to 50 wt%, such as 20 to 50 wt%, such as 30 to 70 wt%, such as 30 to 50 wt%, such as 30 to 40 wt%, based on the total weight of the binder solids.

[0016] The compositions of the present disclosure may further comprise a curing agent. The curing agent comprises functional groups reactive with functional groups on the film-forming resin. Suitable curing agents include at least partially blocked polyisocyanates, aminoplast resins and phenoplast resins, such as phenolformaldehyde condensates including allyl ether derivatives thereof.

[0017] Suitable at least partially blocked polyisocyanates include aliphatic polyisocyanates, aromatic polyisocyanates, and mixtures thereof, including fully blocked aliphatic polyisocyanates, such as those described in U.S. Patent No. 3,984,299 at col. 1 line 57 to col. 3 line 15, this portion of which is incorporated herein by reference, or partially blocked aliphatic polyisocyanates that are reacted with the polymer backbone, such as is described in U.S. Patent No. 3,947,338 at col. 2 line 65 to col. 4 line 30, this portion of which is also incorporated herein by reference. By “blocked” is meant that the isocyanate groups have been reacted with a compound such that the resultant blocked isocyanate group is stable to active hydrogens at ambient temperature but reactive with active hydrogens in the film-forming resin at elevated temperatures, such as 90°C to 200°C. The polyisocyanate curing agent may be a fully blocked polyisocyanate with substantially no free isocyanate groups. Suitable blocking agents are well known.

[0018] The polyisocyanate curing agent may comprise a diisocyanate, higher functional polyisocyanates or combinations thereof. For example, the polyisocyanate curing agent may comprise aliphatic and / or aromatic polyisocyanates. Aliphatic polyisocyanates may include (i) alkylene isocyanates, such as trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (“HDI”), 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, ethylidene diisocyanate, and butylidene diisocyanate, and (ii) cycloalkylene isocyanates, such as 1,3- cyclopentane diisocyanate, 1 ,4-cyclohexane diisocyanate, 1,2-cyclohexane diisocyanate, isophorone diisocyanate, methylene bis(4-cyclohexylisocyanate) (“HMD I”), the cyclo-trimer of 1,6-hexmethylene diisocyanate (also known as the isocyanurate trimer of HDI, commercially available as DESMODUR N3300 from Covestro AG), and meta-tetramethylxylylene diisocyanate (commercially available as TMXDI from Allnex SA). Aromatic polyisocyanates may include (i) arylene isocyanates, such as m-phenylene diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate and 1 ,4-naphthalene diisocyanate, and (ii) alkarylene isocyanates, such as 4,4'-diphenylene methane (“MDI”), 2,4-tolylene or 2,6-tolylene diisocyanate (“TDI”), or mixtures thereof, 4,4-toluidine diisocyanate and xylylene diisocyanate.Triisocyanates, such as triphenyl methane-4,4',4"-triisocyanate, 1 ,3,5-triisocyanato benzene and 2,4,6-triisocyanato toluene, tctraisocyanatcs, such as 4,4'-diphcnyldimcthyl mcthanc-2,2',5,5'- tetraisocyanate, and polymerized polyisocyanates, such as tolylene diisocyanate dimers and trimers and the like, may also be used. The curing agent may comprise a blocked polyisocyanate selected from a polymeric polyisocyanate, such as polymeric HD I, polymeric MDI, polymeric isophorone diisocyanate, and the like. The curing agent may also comprise a blocked trimer of hexamethylene diisocyanate available as DESMODUR N3300 from Covestro AG. Mixtures of polyisocyanate curing agents may also be used.

[0019] The curing agent may comprise a high molecular weight volatile group. A “high molecular weight volatile group” refers to blocking agents and other organic byproducts that are produced and volatilized during cure and that have a molecular’ weight of at least 70 g / mol, such as at least 125 g / mol, such as at least 160 g / mol, such as at least 195 g / mol, such as at least 400 g / mol, such as at least 700 g / mol, such as at least 1000 g / mol, or higher, and may range from 70 to 1,000 g / mol, such as 160 to 1,000 g / mol, such as 195 to 1,000 g / mol, such as 400 to 1,000 g / mol, such as 700 to 1,000 g / mol. For example, the organic byproducts may include alcoholic byproducts resulting from the reaction of the film-forming polymer and an aminoplast or phenoplast curing agent, and the blocking agents may include organic compounds, including alcohols, used to block isocyanato groups of polyisocyanates that are unblocked during cure. For clarity, the high molecular weight volatile groups are covalently bound to the curing agent prior to cure, and explicitly exclude any organic solvents that may be present in the fire-resistant electrodepositable coating composition. Upon curing, the overall pigment-to-binder ratio of the deposited film may increase in the cured film relative to deposited uncured pigment-to-binder ratio in the fire-resistant electrodepositable coating composition because of the loss of a higher mass of the blocking agents and other organic byproducts derived from the curing agent that are volatilized during cure. High molecular weight volatile groups may comprise 5 to 50 wt% of the film-forming binder, such as 7 to 45 wt%, such as 9 to 40 wt%, such as 11 to 35 wt%, such as 13 to 30 wt%, based on the total weight of the fire-resistant electrodepositable binder. The high molecular weight volatile groups and other lower molecular weight volatile organic compounds produced during cure, such as lower molecular weight blocking agents and organic byproducts produced during cure, may be present in an amount such that the relative weight loss of the filmforming binder deposited onto the substrate relative to the weight of the film-forming binderafter cure is an amount of 5 to 50 wt% of the film-forming binder, such as 7 to 45 wt%, such as 9 to 40 wt%, such as 11 to 35 wt%, such as 13 to 30 wt%, based on the total weight of the fire- resistant electrodepositable binder before and after cure.

[0020] The curing agent may comprise an aminoplast resin. Aminoplast resins are condensation products of an aldehyde with an amino- or amido-group carrying substance. Condensation products obtained from the reaction of alcohols and an aldehyde with melamine, urea or benzoguanamine may be used. However, condensation products of other amines and amides may also be employed, for example, aldehyde condensates of triazines, diazines, triazoles, guanidines, guanamines and alkyl- and aryl-substituted derivatives of such compounds, including alkyl- and aryl-substituted ureas and alkyl- and aryl-substituted melamines. Some examples of such compounds are N,N'-dimethyl urea, benzourea, dicyandiamide, formaguanamine, acetoguanamine, ammeline, 2-chloro-4,6-diamino-l,3,5-triazine, 6-methyl-2,4- diamino-l,3,5-triazine, 3,5-diaminotriazole, triaminopyrimidine, 2-mercapto-4,6- diaminopyrimidine, 3,4,6-tris(ethylamino)-l,3,5-triazine, and the like. Suitable aldehydes include formaldehyde, acetaldehyde, crotonaldehyde, acrolein, benzaldehyde, furfural, glyoxal and the like.

[0021] The aminoplast resins may contain methylol or similar alkylol groups, and at least a portion of these alkylol groups may be etherified by a reaction with an alcohol to provide organic solvent- soluble resins. Any monohydric alcohol may be employed for this purpose, including such alcohols as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol and others, as well as benzyl alcohol and other aromatic alcohols, cyclic alcohol such as cyclohexanol, monoethers of glycols such as Cello solves and Carbitols, and halogen-substituted or other substituted alcohols, such as 3-chloropropanol and butoxyethanol.

[0022] Aminoplast resins are widely commercially available, such as those under the trademark CYMELfrom Allnex Belgium SA / NV, such as CYMEL 1130 and 1156, or RESIMENE from INEOS Melamines, such as RESIMENE 750 and 753. Examples of suitable aminoplast resins also include those described in U.S. Patent No. 3,937,679 at col. 16, line 3 to col. 17, line 47, this portion of which being hereby incorporated by reference.

[0023] Phenoplast resins are formed by the condensation of an aldehyde and a phenol. Suitable aldehydes include formaldehyde and acetaldehyde. Methylene-releasing and aldehyde- releasing agents, such as paraformaldehyde and hexamethylene tetramine, may also be utilized asthe aldehyde agent. Various phenols may be used, such as phenol itself, a cresol, or a substituted phenol in which a hydrocarbon radical having either a straight chain, a branched chain or a cyclic structure is substituted for a hydrogen in the aromatic ring. Mixtures of phenols may also be employed. Suitable phenols include p-phenylphenol, p-tert-butylphenol, p-tert-amylphenol, cyclopentylphenol and unsaturated hydrocarbon-substituted phenols, such as the monobutenyl phenols containing a butenyl group in ortho, meta or para position, and where the double bond occurs in various positions in the hydrocarbon chain.

[0024] Suitable aminoplast and phenoplast resins are described in U.S. Patent No. 4,812,215 at col.6, line 20 to col. 7, line 12, the cited portion of which being incorporated herein by reference.

[0025] The curing agent may be present in the cationic electrodepo sitable coating composition in an amount of 5 wt% or greater, such as 10 wt% or greater, such as 20 wt% or greater, such as 25 wt% or greater, and may be present in an amount of 60 wt% or lower, such as 50 wt% or lower, such as 40 wt% or lower, such as 30 wt% or lower, such as in an amount of 5 to 60 wt%, such as 10 to 50 wt%, such as 15 to 40 wt%, such as 5 to 30 wt%, such as 10 to 60 wt%, such as 10 to 50 wt%, such as 10 to 40 wt%, such as 10 to 30 wt%, such as 20 to 60 wt%, such as 20 to 50 wt%, such as 20 to 40 wt%, such as 20 to 30 wt%, such as 25 to 60 wt%, such as 25 to 50 wt%, such as 25 to 40 wt%, such as 25 to 30 wt%, based on the total weight of the resin solids of the fire-resistant electrodepositable coating composition.

[0026] The present coating compositions also comprise a hybrid organic-inorganic material. As used herein, the term “hybrid organic -inorganic material(s)” refers to materials that contain both organic and inorganic moieties. “Organic moiety” or “organic portion” in a hybrid material refers to that portion of the material that includes carbon, hydrogen, oxygen, and / or nitrogen atoms. The “inorganic moiety” or “inorganic portion”, therefore, includes an atom other than any of these, such as, for example, a halogen, sulfur, phosphorus, silicon, and the like; these atoms may also be referred to herein as the “inorganic atom(s)” or like terms.

[0027] The hybrid organic-inorganic material has an inorganic portion having an atom wt% of 0.20 or greater, such as 0.40 or greater, or 0.50 or greater, or 0.80 or greater, up to as much as 5.0 wt%, such as 4.0 wt% or lower, or 2.0 wt% or lower, such as 0.20 to 5.0 or 0.40 to 1.0, where atom weight percent is based on the total solids weight of the composition. Atomwt% is determined by taking the mass fraction of the inorganic atoms in the hybrid mass, and determining what percentage that is of the total solids weight.

[0028] The hybrid organic-inorganic material may include material that functions as an additive in the present compositions; that is, they are not reactive with other coating components. The hybrid organic-inorganic material may also include a material that reacts with the filmforming component; that is, the hybrid material has functionality reactive with functionality on the film-forming resin and / or curing agent and reacts during cure. A hybrid organic-inorganic material that is “reactive with” the film-forming component is therefore one that itself becomes part of the film-forming component.

[0029] The hybrid organic-inorganic material can include an organohalogen compound, a phosphorus-containing resin, such as an organophosphorus compound, a silicone resin, a sulfur- containing resin, a nano-gel (sometimes referred to as an aerogel), or a combination thereof.

[0030] Suitable examples of organohalogen compounds include organochlorines such as chlorendic acid derivatives and chlorinated paraffins; organobromines such as decabromodiphenyl ether (decaBDE), decabromodiphenyl ethane (a replacement for decaBDE), polymeric brominated compounds such as brominated polystyrenes, brominated carbonate oligomers (BCOs), brominated epoxy oligomers (BEOs), tetrabromophthalic anyhydride, tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCD). Such halogenated materials may be used in conjunction with a synergist to enhance their efficiency. Other suitable examples include antimony trioxide, antimony pentaoxide, and sodium antimonate.

[0031] Suitable examples of organophosphorus compounds include triphenyl phosphate (TPP), resorcinol bis(diphenylphosphate) (RDP), bisphenol A diphenyl phosphate (BADP), and tricresyl phosphate (TCP); phosphonates such as dimethyl methylphosphonate (DMMP); phosphinates such as aluminum diethyl phosphinate; and ammonium polyphosphate (APP).

[0032] The hybrid organic-inorganic material may comprise compounds that contain both phosphorus and a halogen. Such compounds include tris(2,3-dibromopropyl) phosphate (brominated tris) and chlorinated organophosphates such as tris(l,3-dichloro-2-propyl)phosphate (chlorinated tris or TDCPP) and tetrakis(2-chlorethyl)dichloroisopentyldiphosphate (V6).

[0033] Suitable silicone resins include those having a main polymer chain comprising alternating silicon-oxygen bonding, such as a polydiorganylsiloxane; the organyl may comprise an alkyl group, an aryl group or combinations thereof. When silicone resin is used, it is used inan amount less than any other film-forming resin or curing agent. That is, the silicone resin is not the main film-forming polymer and may be used in amounts of less than 40 wt%, based on total weight of resin solids.

[0034] The hybrid organic-inorganic material may comprise a sulfur-containing resin. Suitable sulfur-containing resin includes mercaptobenzotriazole MBT.

[0035] Suitable hybrid organic-inorganic materials that are reactive with the filmforming component. This includes, for example, monomeric, oligomeric, or polymeric materials comprising phosphorus that will react with functionality in the film-forming component, such that phosphorus becomes incorporated into the polymer network of the film. A specific example is a phosphatized epoxy polymer, such as the reaction product of an epoxy resin and a phosphoric acid or ester thereof, which reaction can occur in the presence of an alcohol, Further examples include P-H containing phosphine oxides such as dimethylphosphine oxide (DMPO), diphenylphosphine oxide (DPPO), diphenyl phosphate (DPP), 9,10-Dihydro-9-oxa-10- phosphaphenanthrene-10-oxide (DOPO) and derivates of any of these. Another class of reactive organophosphorus compounds for use in the present disclosure includes P-X containing phosphine or phosphine oxides, wherein X is a halogen, such as Cl or Br. Suitable examples of P-X containing reactive organophosphorus compounds include phosphoryl chloride, phosphoryl bromide, phenyl dichlorophosphate (PDCP), diphenyl chlorophosphite (DPCP), 10-chloro-9,10- dihydro-9-oxa-10-phosphaphenanthrene (DOP-C1) and derivatives of any of these. “Derivatives” may include, for example, the reaction product of these compounds with other small molecules.

[0036] The pigment-to-binder ratio (P:B) of the hybrid organic-inorganic material may be less than 0.20:1, such as 0.08:1, less than 0.20 to 0.08:1. When the hybrid organic-inorganic material reacts with the film-forming component, the P:B may be 2:1, such as 0.08 to 2.0:1. P:B refers to the weight ratio of a particular- pigment to the binder solids in the electrocoat bath compositions. In the present disclosure, the pigment may be the hybrid material, the inorganic pigment, both, or any other solid indicated. “Binder solids” includes the solids in the filmforming component (i.e. resin and curing agent), and further includes the solids of any hybrid material that reacts with the film-forming resin and / or curing agent.

[0037] The present ecoat compositions further comprise an inorganic pigment. Such pigments, often referred to as fillers, can include metal hydroxide, such as aluminum hydroxide,aluminum oxide or a hydrate thereof, magnesium hydroxide, a zinc compound such as zinc borate or zinc hydroxystannatc, a metal borate, titanium dioxide, barium sulfate, geopolymers such as alkali aluminosilicate, huntite, hydromagnesite, red phosphorus, boron compounds such as boric acid and borates, such as sodium borate, an organic layered silicate, wallastonite, carbonates such as calcium carbonate and magnesium carbonate, iron oxides, lead oxides, strontium chromate, barium sulfate, boron nitride, silicon nitride, aluminum nitride, boron arsenide, silicon dioxide, titanium oxide, zinc oxide, nickel oxide, copper oxide, tin oxide, silicon carbide, agate, emery, diamond, silver, zinc, copper, gold, carbonyl iron, copper, zinc, aluminum, clay, color pigments such as cadmium yellow, cadmium red, chromium yellow, or a combination thereof. “Clay” can include kaolin, calcined kaolin, smectite, montmorillonite, illite, bentonite and others known in the ait. Particularly suitable is TiCh alone or in combination with a second inorganic pigment, such as zinc oxide and / or a clay.

[0038] The atom weight percent of inorganic pigment in the composition is at least 8 wt% or greater, such as 10 wt% or greater, or 20 wt% or lower, such as 15 wt% or lower, or 8 to 20 wt% or 10 to 15 wt%, where weight percent is based on the total solids weight of the composition. Atom weight, when referring to the inorganic pigment, is determined by taking the weight fraction of the inorganic pigment in the total solids.

[0039] The fire-resistant electrodepositable coating composition according to the present disclosure may optionally comprise one or more further components in addition to those described above, including such ingredients commonly used in ecoat formulation. Examples include fillers, plasticizers, antioxidants, biocides, UV light absorbers and stabilizers, hindered amine light stabilizers, defoamers, fungicides, dispersing aids, flow control agents, surfactants, wetting agents, or combinations thereof. These additives may be present in the fire-resistant electrodepositable coating composition in amounts of 0.01 to 3 wt%, based on total solids weight of the composition.

[0040] The fire-resistant electrodepositable coating composition according to the present disclosure may optionally comprise a compound that generates an expansion gas upon thermal decomposition. Suitable examples include melamine and its derivatives, ammonium salts of phosphoric acid, guanidine, methylolated melamine, hexamethoxymethyl melamine, urea, dimethylurea, melamine pyrophosphate, dicyandiamide, guanylurea phosphate, glycine, calcium carbonate, magnesium carbonate, calcium hydroxide, magnesium dihydroxide, aluminumtrihydroxide, boric acid and boric acid esters. Tt will be appreciated that some of these compounds arc also “hybrid organic-inorganic materials” or “inorganic pigments” and so they may have more than one function in the coating and should be considered when calculating atom wt%. If used, the compound that generates an expansion gas upon thermal decomposition can be used in any desired amount, depending on the amount of expansion of the coating char desired. For example, due to space constraints, it may be desired to use the expansion gas generator in quantities that provide for no more than five times expansion; when no space constraints exist, greater than five times expansion, such as ten times, twenty times, or even greater may be desired.

[0041] The fire-resistant electrodepositable coating compositions may further comprise an aqueous medium. An “aqueous medium” is one comprising water and optionally one or more organic solvent(s). The aqueous medium may be present in amounts of, for example, 40 to 90 wt%, such as 50 to 85 wt%, based on total weight of the composition. The fire-resistant electrodepositable coating composition may be in the form of an aqueous dispersion; an “aqueous dispersion” means the particles of the ecoat compositions as described herein are dispersed in the aqueous medium.

[0042] Examples of suitable organic solvents include oxygenated organic solvents, such as monoalkyl ethers of ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol which contain from 1 to 10 carbon atoms in the alkyl group, such as the monoethyl and monobutyl ethers of these glycols. Examples of other at least partially water- miscible solvents include alcohols such as ethanol, isopropanol, butanol and diacetone alcohol. If used in the aqueous medium, the organic solvents may typically be present in an amount of less than 10 wt%, such as less than 5 wt%, based on total weight of the fire-resistant electrodepositable coating composition.

[0043] According to the present disclosure, the total solids content of the fire-resistant electrodepositable coating composition may be 1 wt% or greater, such as 5 wt% or greater, and may be 50 wt% or lower, such as 40 wt% or lower, such as 20 wt% or lower, based on the total weight of the fire-resistant electrodepositable coating composition. The total solids content of the fire-resistant electrodepositable coating composition may be from 1 to 50 wt%, such as 5 to 40 wt%, such as 5 to 20 wt%, based on the total weight of the fire-resistant electrodepositable coating composition. The “total solids” or “total solids weight” of the composition refers to thenon-volatile content of the fire-resistant electrodepositable coating composition, i.e., materials that will not volatilize when heated to 110°C for 15 minutes.

[0044] The cationic electrodepo sitable coating composition may have a pH of 3.0 to 6.5, 3.0 to 6.0, such as such as 3.0 to 5.5, such as 3.0 to 5.0, such as 3.0 to 4.5, such as 3.0 to 4.0, such as 3.0 to 3.5, such as 3.5 to 6.5, such as 3.5 to 6.0, such as 3.5 to 5.5, such as 3.5 to 5.0, such as 3.5 to 4.5, such as 3.5 to 4.0, such as 4.0 to 6.5, such as 4.0 to 6.0, such as 4.0 to 5.5, such as 4.0 to 5.0, such as 4.0 to 4.5.

[0045] According to the present disclosure, the fire-resistant electrodepo sitable coating composition may comprise a catalyst to catalyze the reaction between the curing agent and the film-forming resin. Examples of catalysts suitable for cationic electrodepositable coating compositions include organotin compounds (e.g., dibutyltin oxide and dioctyltin oxide) and salts thereof (e.g., dibutyltin diacetate); other metal oxides (e.g., oxides of cerium, zirconium and bismuth) and salts thereof (e.g., bismuth sulfamate and bismuth lactate); or a cyclic guanidine as described in U.S. Pat. No. 7,842,762 at col. 1, line 53 to col. 4, line 18 and col. 16, line 62 to col. 19, line 8, the cited portions of which being incorporated herein by reference.

[0046] The fire-resistant electrodepositable coating composition may be substantially free, essentially free, or completely free of tin. As used herein, an electrodepositable coating composition is substantially free of tin if tin is present in an amount of less than 0.1 wt%, based on the total weight of the resin blend solids. As used herein, an electrodepositable coating composition may be essentially free of tin if tin is present in an amount of less than 0.01 wt%, based on the total weight of the resin blend solids. As used here, an electrodepositable coating composition is completely free of tin if tin is not present in the composition, i.e., 0.00 wt%, based on the total resin blend solids.

[0047] The fire-resistant electrodepositable coating composition may be substantially free, essentially free, or completely free of bismuth. As used herein, an electrodepositable coating composition is substantially free of bismuth if bismuth is present in an amount of less than 0.1 wt%, based on the total weight of the resin blend solids. As used herein, an electrodepositable coating composition may be essentially free of bismuth if bismuth is present in an amount of less than 0.01 wt%, based on the total weight of the resin blend solids. As used here, an electrodepositable coating composition is completely free of bismuth if bismuth is not present in the composition, i.e., 0.00 wt%, based on the total resin blend solids.

[0048] The fire-resistant electrodepositable coating composition may be substantially free, essentially free, or completely free of metal pigment. As used herein, the term “metal pigment” refers to metal and metal alloy pigments that consist primarily of metal(s) in the elemental (zerovalent) state. The metal particles may include zinc, aluminum, cadmium, magnesium, beryllium, copper, silver, gold, iron, titanium, nickel, manganese, chromium, scandium, yttrium, zirconium, platinum, tin, and alloys thereof, as well as various grades of steel. As used herein, an electrodepositable coating composition is substantially free of metal pigment if metal pigment is present in an amount of less than 5 wt%, based on the total weight of the pigment of the composition. As used herein, an electrodepositable coating composition is essentially free of metal pigment if metal pigment is present in an amount of less than 1 wt%, based on the total weight of the pigment of the composition. As used here, an electrodepositable coating composition is completely free of metal pigment if metal pigment is not present in the composition, i.e., 0.00 wt%, based on the total weight of the pigment of the composition.

[0049] The fire-resistant electrodepositable coating composition may be substantially free, essentially free, or completely free of mica. As used herein, an electrodepositable coating composition is substantially free of mica if mica is present, if at all, in an amount of less than 1 wt%, based on the total solids weight of the composition. As used herein, an electrodepositable coating composition is essentially free of mica if mica is present, if at all, in an amount of less than 0.1 wt%, based on the total solids weight of the composition. As used here, an electrodepositable coating composition is completely free of mica if mica is not present in the composition, i.e., 0.00 wt%, based on the total solids weight of the composition.

[0050] The fire-resistant electrodepositable coating composition may be substantially free, essentially free, or completely free of aluminum oxide. As used herein, an electrodepositable coating composition is substantially free of aluminum oxide if aluminum oxide is present, if at all, in an amount of less than 1 wt%, based on the total solids weight of the composition. As used herein, an electrodepositable coating composition is essentially free of aluminum oxide if aluminum oxide is present, if at all, in an amount of less than 0.1 wt%, based on the total solids weight of the composition. As used here, an electrodepositable coating composition is completely free of aluminum oxide if aluminum oxide is not present in the composition, i.e., 0.00 wt%, based on the total solids weight of the composition.

[0051] The fire-resistant electrodepositable coating composition may be substantially free, essentially free, or completely free of inorganic glass particles. As used herein, an electrodepositable coating composition is substantially free of inorganic glass particles if inorganic glass particles are present, if at all, in an amount of less than 5 wt%, based on the total solids weight of the composition. As used herein, an electrodepositable coating composition is essentially free of inorganic glass particles if inorganic glass particles are present, if at all, in an amount of less than 1 wt%, based on the total solids weight of the composition. As used here, an electrodepositable coating composition is completely free of inorganic glass particles if inorganic glass particles are not present in the composition, i.e., 0.00 wt%, based on the total solids weight of the composition.

[0052] The fire-resistant electrodepositable coating composition may be substantially free, essentially free, or completely free of melamine and / or a melamine derivative. As used herein, an electrodepositable coating composition is substantially free of melamine and / or a melamine derivative if melamine and / or a melamine derivative is present, if at all, in an amount of less than 5 wt%, based on the total solids weight of the composition. As used herein, an electrodepositable coating composition is essentially free of melamine and / or a melamine derivative if melamine and / or a melamine derivative is present, if at all, in an amount of less than 1 wt%, based on the total solids weight of the composition. As used here, an electrodepositable coating composition is completely free of melamine and / or a melamine derivative if melamine and / or a melamine derivative is not present in the composition, i.e., 0.00 wt%, based on the total solids weight of the composition.

[0053] The fire-resistant electrodepositable coating composition may be substantially free, essentially free, or completely free of phenoplast resin. As used herein, an electrodepositable coating composition is substantially free of phenoplast resin if phenoplast resin is present, if at all, in an amount of less than 5 wt%, based on the total solids weight of the composition. As used herein, an electrodepositable coating composition is essentially free of phenoplast resin if phenoplast resin is present, if at all, in an amount of less than 1 wt%, based on the total solids weight of the composition. As used here, an electrodepositable coating composition is completely free of phenoplast resin if phenoplast resin is not present in the composition, i.e., 0.00 wt%, based on the total solids weight of the composition.

[0054] The fire-resistant electrodepositable coating composition may optionally further comprise a resin containing sulfonate or phosphonatc in an amount of more than 3 wt%, based on resin solids weight, such as more than 5 wt%, such as more than 10 wt%.

[0055] The present disclosure is also directed to a method for using any of the coating compositions described herein to coat at least a portion of a substrate, comprising depositing any such composition on the substrate through electrophoretic means. Accordingly, the present disclosure is further directed to a substrate that is coated, at least in part, by this method.

[0056] Any substrates known in the art can be coated according to the present methods, for example, automotive substrates, marine substrates, industrial substrates, heavy-duty equipment, packaging substrates, electronics including housings and circuit boards and including consumer electronics such as housings for computers, notebooks, smartphones, tablets, televisions, gaming equipment, computer equipment, computer accessories, MP3 players, glass and transparencies, sports equipment and the like. These substrates can be, for example, metallic or non-metallic. Metallic substrates include metal sheet, tin, steel, tin-plated steel, chromium passivated steel, galvanized steel, aluminum, and aluminum foil. Metal sheet as used herein refers to flat metal sheet and coiled metal sheet, which is coiled, uncoiled for coating, and then re-coiled for shipment to a manufacturer. Non-metallic substrates include polymeric, plastic, polyester, polyolefin, polyamide, cellulosic, polystyrene, polyacrylic, poly(ethylene naphthalate), polypropylene, polyethylene, nylon, EVOH, polylactic acid, other “green” polymeric substrates, poly(ethyleneterephthalate) (“PET”) including post-consumer or recycled PET (“rPET”), polycarbonate, polycarbonate acrylobutadiene styrene (“PC / ABS”), SMC, carbon fiber, polyamide, cement, stone, glass, and the like that have been metalized in some way so as to be conductive, such as nickel-plated plastic. Additionally, substrates may comprise non-metal conductive materials including composite materials such as, for example, materials comprising carbon fibers or conductive carbon and / or otherwise reinforced, such as with fiberglass, or Kevlar.

[0057] The metal or metal alloy substrates of the present disclosure may comprise cold rolled steel, hot rolled steel, steel coated with zinc metal, zinc compounds, or zinc alloys, such as electrogalvanized steel, hot-dipped galvanized steel, galvanealed steel, and steel plated with zinc alloy. Aluminum alloys of the 2XXX, 3XXX, 4XXX, 5XXX, 6XXX, or 7XXX series as well as clad aluminum alloys and cast aluminum alloys of the A356 series also may be used as thesubstrate. Magnesium alloys of the AZ31B, AZ91C, AM60B, or EV31 A series also may be used as the substrate. The substrate used in the present disclosure may also comprise titanium and / or titanium alloys. Other suitable non-ferrous metals include copper and magnesium, as well as alloys of these materials.

[0058] Suitable substrates for use in the present disclosure include those that are used in the form of sheets or coils, or in the assembly of appliances or of vehicular bodies (for example., door, body panel, trunk deck lid, roof panel, hood, roof and / or stringers, rivets, landing gear components, and / or skins used on an aircraft), vehicular' frames, vehicular- parts, motorcycles, wheels, and industrial structures and components. As used herein, “vehicle” refers to in its broadest sense all types of vehicles, including conventional, electrical and hybrid vehicles, such as cars, trucks, buses, tractors, harvesters, heavy duty equipment, vans, golf carts, motorcycles, bicycles, e-bikes, railcars, subway cars, airplanes, helicopters, boats of all sizes and the like. For example, a vehicle may be an aerospace vehicle including aircraft such as airplanes including private aircraft, and small, medium, or large commercial passenger, freight, civilian and military aircraft; helicopters, including private, commercial, and military helicopters; or rockets and other spacecraft. A vehicle can include a ground vehicle such as, for example, tanks, armored car's, trailers, cars, trucks, buses, vans, construction vehicles, golf carts, motorcycles, bicycles, electric bicycles, trains, and railroad cars. A vehicle can also include watercraft such as, for example, ships, boats, and hovercraft. The fire-resistant electrodepositable coating composition may be utilized to coat surfaces and parts thereof. A part may include multiple surfaces. A part may include a portion of a larger pail, assembly, or apparatus. A portion of a part may be coated with the coating composition of the present disclosure, or the entire part may be coated. The metal substrate also may be in the form of, for example, a sheet of metal or a fabricated part.

[0059] The substrate may comprise a three-dimensional component formed by an additive manufacturing process, provided the substrate is conductive or made conductive such as through metallization.

[0060] The substrate may be a multi-metal article. As used herein, the term “multi-metal article” refers to (1) an article that has at least one surface comprised of a first metal and at least one surface comprised of a second metal that is different from the first metal, (2) a first article that has at least one surface comprised of a first metal and a second article that has at least one surface comprised of a second metal that is different from the first metal, or (3) both (1) and (2).The substrate may comprise surfaces or parts of different substrate materials that are adjacent or joined together such as, for example, a galvanic assembly.

[0061] It will also be understood that the substrate may be pretreated with a pretreatment solution including a zinc phosphate pretreatment solution such as, for example, those described in U.S. Patent Nos. 4,793,867 and 5,588,989, or a zirconium containing pretreatment solution such as, for example, those described in U.S. Patent Nos. 7,749,368 and 8,673,091.

[0062] The substrate may comprise an energy storage device, such as a battery or battery component. The battery may be, for example, an electric vehicle battery, and the battery component may be an electric vehicle battery component. A “battery component” may be any component found in a battery, such as a lithium-ion battery. The battery component may comprise, for example, an electrode, a battery cell, a battery shell, a battery module, a battery pack, a battery box, a battery cell casing, a pack shell, a battery lid and tray, a thermal management system, a battery housing, a module housing, a module racking, a battery side plate, a battery cell enclosure, a cooling module, a cooling tube, a cooling fin, a cooling plate, a bus bar, a battery frame, an electrical connection, metal wires, or copper or aluminum conductors or cables. Other energy storage devices include, but are not limited to, fuel cells or hydrogen tanks.

[0063] When substrates coated according to the present disclosure include a battery component, it might be desirable to use one or more additional fire-retardant materials and / or fire mitigation means within and / or around the battery. For example, a thermally insulating material or a high strength material could be wrapped around or otherwise positioned between battery cells, or around the perimeter or interior of the battery housing. Examples of such material include fiberglass, mineral wool, silica / silica fibers, alumina, Kevlar, Nomex, calcium- silicate, or calcium silicate fibers; these materials can be, for example, in a sheet or other self-supported form. Foams could also be used, such as polyurethane / polyurea foam with fire retardants. Physical barriers could also be employed, such as cooling fins interposed between battery cells, mica boards, Aerogel blankets, and / or mineral / glass / carbon fiber-containing blankets.

[0064] To provide fire protection for articles comprising a battery and their users it is also within the present disclosure to apply the present ecoat composition to a part of an article adjacent to the battery, such as between the battery and the article, to insulate the article from the battery. “Between” when referring to the coating layer being deposited between the article, such as a vehicle, and the battery, does not exclude one or more additional coating layers or other firemitigation means also between the article and the battery. In such cases a conventional battery or a battery according to the present disclosure can be employed. The article may be, for example, a mobile phone, a tablet, a laptop computer or a vehicle.

[0065] As noted above, the vehicle may be a hybrid or electric car, bus or truck. In such vehicles it is common to position the battery, due to its weight, as a flat battery pack underneath the floor portion of the vehicle body, such as the car body. The ecoat composition of the present disclosure may be applied to the portion of the vehicle adjacent to the battery, such as between the battery and the vehicle. In an event of a thermal runaway of the battery or a battery fire, the car body, especially the passenger cabin, would be protected so that the battery box will resist flame, and any fire inside the battery box will not spread into the passenger cabin; heat-up of the passenger cabin may also be limited for a prolonged period of time so that the passengers can safely escape from the vehicle in case of such an incident.

[0066] It may be desirable to apply the fire-resistant ecoat compositions of the present disclosure to a vehicle comprising an electric battery, particularly the area in contact with or adjacent the battery. This can be in addition to, or instead of, coating any of the battery components. Alternatively, other fire-resistant ecoat compositions can be used to coat the vehicle surface, such as those disclosed in U.S. Patent No. 10,697,081; U.S. Pub. No. 2023 / 044601 Al, Inf 1 Pub. No. 2021 / 127327A1; and Inf 1 Pub. No. 2022 / 133202 Al. Fire- retardant adhesives, sealants, gap fillers, pottants, and encapsulants can also be used in the vehicle, such as those formed from a composition comprising a fire-retardant. Fire retardants may be available as a powder that may be mixed with a composition, a foam, or a gel that may form a coating that may impart fire-retardants to a substrate surface. Suitable examples include those disclosed above as well as those disclosed in Inf 1 Publ. No. 2021211722A1, pars. 57-309; Int’l Publ. No. 2021211183A1, par's. 44-178; Int’l Publ. No. 2021211184A1, par's. 52-252; Int’l Publ. No. 2021211694A1, par's. 60-299; PCT Appn. No. PCT / 23 / 67964, pars. 44-183; U.S. Provisional Appn. No. 63 / 505,645, pars. 51-252; U.S. Provisional Appn. No. 63 / 497,303, pars. 31-141; and U.S. Provisional Appn. No. 63 / 477,568, pars. 58-223.

[0067] According to the present disclosure, the cationic electrodepo sitable coating composition of the present disclosure may be deposited upon an electrically conductive substrate by placing the composition in contact with an electrically conductive cathode and an electrically conductive anode, with the surface to be coated being the cathode. Following contact with thecomposition, an adherent film of the coating composition is deposited on the cathode when a sufficient voltage is impressed between the electrodes. The conditions under which the electrodeposition is carried out are, in general, similar to those used in electrodeposition of other types of coatings. The applied voltage may be varied and can be, for example, as low as one volt to as high as several thousand volts, such as 50 to 500 volts. The current density may be 0.5 ampere to 15 amperes per square foot and tends to decrease during electrodeposition indicating the formation of an insulating film.

[0068] Once the fire-resistant electrodepositable coating composition is electrodeposited over at least a portion of the electroconductive substrate, the coated substrate is heated to a temperature and for a time sufficient to at least partially cure the electrodeposited coating on the substrate. As used herein, the term “at least partially cured” with respect to a coating refers to a coating formed by subjecting the coating composition to curing conditions such that a chemical reaction of at least a portion of the reactive groups of the components of the coating composition occurs to form a coating. The coated substrate may be heated to a temperature ranging from 250°F to 450°F (121.1°C to 232.2°C), such as from 275°F to 400°F (135°C to 204.4°C), such as from 300°F to 360°F (149°C to 180°C). The curing time may be dependent upon the curing temperature as well as other variables, for example, the film thickness of the electrodeposited coating, level and type of catalyst present in the composition and the like. For purposes of the present disclosure, all that is necessary is that the time be sufficient to effect cure of the coating on the substrate. For example, the curing time can range from 10 minutes to 60 minutes, such as 20 to 40 minutes. The thickness of the resultant cured electrodeposited coating may range from 10 to 50 microns.

[0069] The fire-resistant electrodepositable coating compositions of the present disclosure may also, if desired, be applied to a substrate using non-electrophoretic coating application techniques, such as flow, dip, spray and roll coating applications. For non- electrophoretic coating applications, the coating compositions may be applied to conductive substrates as well as non-conductive substrates such as glass, wood and plastic.

[0070] The fire-resistant electrodepositable coating compositions of the present disclosure may be used as pail of a multi-layer coating system wherein the electrodeposited coating layer deposited from the present electrodepositable composition may have one or more additional coating layers deposited over the electrodeposited coating layer. The coating systemmay comprise a pretreatment layer, such as a phosphate layer (e.g., zinc phosphate layer), and the fire-resistant clcctrodcpositablc coating composition described in the present disclosure may be deposited over at least a portion of the pretreated layer; one or more additional coating layers may be applied over at least a portion of the electrodeposited coating layer. The one or more additional coating layers may comprise primers, basecoats, color coats, monocoats, clear coats and / or topcoats. Suitable additional coating layers include any of those known in the art, and each independently may be waterborne, solventborne, in solid particulate form (i.e., a powder coating composition), or in the form of a powder slurry. The additional coating layers may each be cured independently, or optionally applied “wet-on-wet” and cured simultaneously. As used herein, “wet-on- wet” refers to a process, wherein a coating, for example a clear coat, is applied over a substantially uncured different coating layer, for example a color coat, and both coatings are then cured simultaneously. In another example, a fire-resistant coating composition, such as, a fire-resistant powder coating composition, may be applied over at least a part of the system comprising the electrocoat coating composition. Suitable powder coating compositions that may be used as an additional coat over the electrodeposited coating layer of the present disclosure include, but are not limited to, those described in Int’l Pub. No. WO 2021 / 173941 Al and Int’l Pub. No. WO 2018 / 187755 Al, each of which are incorporated herein by reference. Suitable intumescent coating compositions include, but are not limited to, those disclosed in Int’l Pub. No. 2020 / 047059 Al, which is incorporated herein by reference. Use of the present coating layers in conjunction with one or more of the coating layers described herein is referred to as a “coating stack”.

[0071] As used herein, unless otherwise defined, the term “substantially free” means that the component is present, if at all, in an amount of less than 1 wt%, based on the total resin solids weight of the composition.

[0072] As used herein, unless otherwise defined, the term “essentially free” means that the component is present, if at all, in an amount of less than 0.1 wt%, based on the total resin solids weight of the composition.

[0073] As used herein, unless otherwise defined, the term completely free means that the component is not present in the composition, i.e., 0.00 wt%, based on the total resin solids weight of the composition.

[0074] Any numerical range recited herein is intended to include all sub-ranges subsumed therein. Singular’ encompasses plural and vice versa. For example, although reference is made herein to “a” film-forming component, “a” film-forming resin, “a” curing agent, “a” hybrid organic-inorganic material, “an” inorganic pigment, and the like, one or more of each of these and any other components can be used. Also, as used herein, the term “polymer” refers to prepolymers, oligomers and both homopolymers and copolymers; the prefix “poly” refers to two or more. When ranges are given, any endpoints of those ranges and / or numbers within those ranges can be combined with the scope of the present disclosure. “Including”, “such as”, “for example” and like terms means “including / such as / for example but not limited to”. “(Meth)acrylic” and like terms refer to both methacrylic and acrylic acid. The terms “acrylic” and “acrylate” may be used interchangeably (unless to do so would alter the intended meaning) and include acrylic acids, anhydrides, and derivatives thereof, lower alkyl-substituted acrylic acids, e.g., C1-C2 substituted acrylic acids, such as methacrylic acid, methacrylic acid, etc., and their Ci-Ce alkyl esters and hydroxyalkyl esters, unless clearly indicated otherwise.Aspects:

[0075] Aspect 1. A cationic fire-resistant electrodepositable coating composition comprising a film-forming component; a hybrid organic-inorganic material, wherein the inorganic portion of the hybrid has an atom wt% of 0.20 or greater based on total solids weight of the composition and has a P:B of less than 0.20:1; and an inorganic pigment, wherein the inorganic pigment has an atom wt % of 8.0 wt% or greater based on total solids weight of the composition

[0076] Aspect 2. The composition of aspect 1, wherein the hybrid organic-inorganic material has a P:B of 0.08:1

[0077] Aspect 3. The composition of aspect 1 or 2, wherein the hybrid organic- inorganic material has a P:B of 0.20 to 0.08:1.

[0078] Aspect 4. A cationic fire-resistant electrodepositable coating composition comprising a film-forming component;a hybrid organic-inorganic material that is reactive with the film-forming component, wherein the inorganic portion of the hybrid has an atom wt% of 0.20 or greater based on total solids weight of the composition; and an inorganic pigment, wherein the inorganic pigment has an atom wt% of 8.0 wt% or greater based on total solids weight of the composition.

[0079] Aspect 5. The composition of aspect 4, wherein the hybrid organic-inorganic material has a P:B of 0.08 to 2:1.

[0080] Aspect 6. The composition of aspects 4 to 5, wherein the hybrid material comprises a monomeric, oligomeric, or polymeric material comprising phosphorus that will react with functionality in the film-forming component, such that phosphorus becomes incorporated into the polymer network of the film.

[0081] Aspect 7. The composition of aspect 6, wherein the hybrid material comprises phosphatized epoxy.

[0082] Aspect 8. The composition of aspect 6, wherein the hybrid material comprises a phosphine oxide of the general formula P-H.

[0083] Aspect 9. The composition of aspect 8, wherein the hybrid material comprises dimethylphosphine oxide (DMPO) and derivatives thereof.

[0084] Aspect 10. The composition of aspect 8, wherein the hybrid material comprises diphenylphosphine oxide (DPPO) and derivatives thereof.

[0085] Aspect 11. The composition of aspect 8, wherein the hybrid material comprises diphenyl phosphate (DPP) and derivatives thereof.

[0086] Aspect 12. The composition of aspect 8, wherein the hybrid material comprises 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and derivatives thereof.

[0087] Aspect 13. The composition of aspect 6, wherein the hybrid material comprises a phosphine or phosphine oxide of the general formula P-X, where X is a halogen such as Cl or Br.

[0088] Aspect 14. The composition of aspect 13, wherein the hybrid material comprises phosphoryl chloride.

[0089] Aspect 15. The composition of aspect 13, wherein the hybrid material comprises phosphoryl bromide.

[0090] Aspect 16. The composition of aspect 13, wherein the hybrid material comprises phenyl dichloropho sphatc (PDCP) and derivatives thereof.

[0091] Aspect 17. The composition of aspect 13, wherein the hybrid material comprises phenyl dichlorophosphate (PDCP) and derivatives thereof.

[0092] Aspect 18. The composition of aspect 13, wherein the hybrid material comprises diphenyl dichlorophosphite (DPCP) and derivatives thereof.

[0093] Aspect 19. The composition of aspect 13, wherein the hybrid material comprises 10-chloro-9,10-dihydro-9-oxa-10-phosphaphenanthrene (DOP-C1) and derivatives thereof.

[0094] Aspect 20. The composition of any preceding aspect, wherein the filmforming component comprises a film-forming resin and a curing agent.

[0095] Aspect 21. The composition of aspect 20, wherein the film-forming resin comprises an amine functional resin and the curing agent comprises a blocked isocyanate.

[0096] Aspect 22. The composition of aspect 20, wherein the curing agent comprises an aminoplast.

[0097] Aspect 23. The composition of aspects 20 to 22, wherein the composition comprises 5 wt% or greater film-forming resin, based on total binder solids.

[0098] Aspect 24. The composition of aspects 20 to 22, wherein the composition comprises 20 wt% or greater film- forming resin, based on total binder solids.

[0099] Aspect 25. The composition of aspects 20 to 22, wherein the composition comprises 30 wt% or greater film- forming resin, based on total binder solids.

[0100] Aspect 26. The composition of aspects 20 to 25, wherein the composition comprises 100 wt% or lower film-forming resin, based on total binder solids.

[0101] Aspect 27. The composition of aspects 20 to 25, wherein the composition comprises 60 wt% or lower film-forming resin, based on total binder solids.

[0102] Aspect 28. The composition of aspects 20 to 25, wherein the composition comprises 50 wt% or lower film-forming resin, based on total binder solids.

[0103] Aspect 29. The composition of aspects 20 to 25, wherein the composition comprises 40 wt% or lower film-forming resin, based on total binder solids.

[0104] Aspect 30. The composition of aspects 20 to 29, wherein the composition comprises 5 to 100 wt% film-forming resin, based on total binder solids.

[0105] Aspect 31 . The composition of aspects 20 to 29, wherein the composition comprises 10 to 60 wt% film- forming resin, based on total binder solids.

[0106] Aspect 32. The composition of aspects 20 to 29, wherein the composition comprises 5 to 40 wt% film-forming resin, based on total binder solids.

[0107] Aspect 33. The composition of aspects 20 to 29, wherein the composition comprises 5 to 30 wt% film-forming resin, based on total binder solids.

[0108] Aspect 34. The composition of aspects 20 to 29, wherein the composition comprises 20 to 40 wt% film- forming resin, based on total binder solids.

[0109] Aspect 35. The composition of aspects 20 to 34, wherein the composition comprises 5 wt% or greater curing agent, based on total binder solids.

[0110] Aspect 36. The composition of aspects 20 to34, wherein the composition comprises 10 wt% or greater curing agent, based on total binder solids.

[0111] Aspect 37. The composition of aspects 20 to 34, wherein the composition comprises 15 wt% or greater curing agent, based on total binder solids.

[0112] Aspect 38. The composition of aspects 20 to 34, wherein the composition comprises 60 wt% or lower curing agent, based on total binder solids.

[0113] Aspect 39. The composition of aspects 20 to 38, wherein the composition comprises 5 to 60 wt% curing agent, based on total binder solids.

[0114] Aspect 40. The composition of aspects 20 to 38, wherein the composition comprises 10 to 50 wt% curing agent, based on total binder solids.

[0115] Aspect 41. The composition of aspects 20 to 38, wherein the composition comprises 15 to 40 wt% curing agent, based on total binder solids.

[0116] Aspect 42. The composition of any preceding aspect, wherein the inorganic portion of the hybrid has an atom wt% of 0.40 or greater based on total solids weight of the composition.

[0117] Aspect 43. The composition of any preceding aspect, wherein the inorganic portion of the hybrid has an atom wt% of 0.50 or greater based on total solids weight of the composition.

[0118] Aspect 44. The composition of any preceding aspect, wherein the inorganic portion of the hybrid has an atom wt% of 0.80 or lower based on total solids weight of the composition.

[0119] Aspect 45. The composition of any preceding aspect, wherein the inorganic portion of the hybrid has an atom wt% of 5.0 wt% or lower based on total solids weight of the composition.

[0120] Aspect 46. The composition of any preceding aspect, wherein the inorganic portion of the hybrid has an atom wt% of 4.0 wt% or lower based on total solids weight of the composition.

[0121] Aspect 47. The composition of any preceding aspect, wherein the inorganic portion of the hybrid has an atom wt% of 2.0 wt% or lower based on total solids weight of the composition.

[0122] Aspect 48. The composition of any preceding aspect, wherein the inorganic portion of the hybrid has an atom wt% of 0.20 to 5.0 based on total solids weight of the composition.

[0123] Aspect 49. The composition of any preceding aspect, wherein the inorganic portion of the hybrid has an atom wt% of 0.40 to 1.0 based on total solids weight of the composition.

[0124] Aspect 50. The composition of any preceding aspect, wherein the hybrid organic-inorganic material comprises an organohalogen compound.

[0125] Aspect 51. The composition of any preceding aspect, wherein the hybrid organic-inorganic material comprises an organophosphorus compound.

[0126] Aspect 52. The composition of any preceding aspect, wherein the hybrid organic-inorganic material comprises a silicone resin.

[0127] Aspect 53. The composition of aspect 52, wherein the silicone resin comprises a polydiorganylsiloxane.

[0128] Aspect 54. The composition of aspects 52 to 53, wherein the composition comprises less than 40 wt% silicone resin, based on total binder solids.

[0129] Aspect 55. The composition of any preceding aspect, wherein the hybrid organic-inorganic material comprises a sulfur-containing resin.

[0130] Aspect 56. The composition of aspect 55, wherein the sulfur-containing composition comprises mercaptobenzotriazole.

[0131] Aspect 57. The composition of any preceding aspect, wherein the inorganic pigment comprises TiC .

[0132] Aspect 58. The composition of any preceding aspect, wherein the pigment comprises TiCh and a second inorganic pigment.

[0133] Aspect 59. The composition of any preceding aspect, wherein the inorganic pigment comprises TiCT and zinc oxide.

[0134] Aspect 60. The composition of any preceding aspect, wherein the inorganic pigment comprises TiCT and clay.

[0135] Aspect 61. The composition of any preceding aspect, wherein the inorganic pigment has an atom wt% of 10.0 wt% or greater, with wt% based on total solids weight of the composition.

[0136] Aspect 62. The composition of any preceding aspect, wherein the inorganic pigment has an atom wt% of 20 wt% or lower, based on total solids weight of the composition.

[0137] Aspect 63. The composition of any preceding aspect, wherein the pigment has an atom wt% of 15 wt% or lower, based on total solids weight of the composition.

[0138] Aspect 64. The composition of any preceding aspect, wherein the inorganic pigment has an atom wt% of 8 to 20 wt%, based on total solids weight of the composition.

[0139] Aspect 65. The composition of any preceding aspect, wherein the inorganic pigment has an atom wt% of 10 to 15 wt%, based on total solids weight of the composition.

[0140] Aspect 66. The composition of any preceding aspect, wherein the composition further comprises a compound that generates an expansion gas upon thermal decomposition.

[0141] Aspect 67. The composition of aspect 66, wherein the additive comprises melamine or melamine derivatives.

[0142] Aspect 68. The composition of any preceding aspect further comprising an aqueous medium.

[0143] Aspect 69. The composition of any preceding aspect, wherein the cationic, fire-resistant ecoat composition is in the form of an aqueous dispersion.

[0144] Aspect 70. The composition of any preceding aspect, wherein the composition is substantially free, essentially free or completely free of tin.

[0145] Aspect 71. The composition of any preceding aspect, wherein the composition is substantially free, essentially free or completely free of bismuth.

[0146] Aspect 72. The composition of any preceding aspect, wherein the composition is substantially free, essentially free or completely free of metal pigment.

[0147] Aspect 73. The composition of any preceding aspect, wherein the composition is substantially free, essentially free or completely free of mica.

[0148] Aspect 74. The composition of any preceding aspect, wherein the composition is substantially free, essentially free or completely free of aluminum oxide.

[0149] Aspect 75. The composition of any preceding aspect, wherein the composition is substantially free, essentially free or completely free of inorganic glass particles.

[0150] Aspect 76. The composition of any preceding aspect, wherein the composition is substantially free, essentially free or completely free of melamine or derivatives thereof.

[0151] Aspect 77. The composition of any preceding aspect, wherein the composition is substantially free, essentially free or completely free of phenoplast resin.

[0152] Aspect 78. A coating layer deposited from any of aspects 1 to 77, wherein the layer, when cured to a DFT of 0.8 to 1.0 mils does not ignite when exposed to the DIRECT FIREEXPOSURE TEST.

[0153] Aspect 79. The coating layer of aspect 78, wherein the film loss is less than 7 mm.

[0154] Aspect 80. The coating layer of aspect 78, wherein the film loss is 6mm or less.

[0155] Aspect 81. The coating layer of aspect 78, wherein the film loss is 2mm or less.

[0156] Aspect 82. A method of using the composition of any of aspects 1 to 77 to coat at least a portion of a substrate, comprising depositing any such composition on the substrate through electrophoretic means.

[0157] Aspect 83. A substrate coated at least in part by the method of aspect 82.

[0158] Aspect 84. The substrate of aspect 82, wherein the substrate is metallic.

[0159] Aspect 85. The substrate of aspect 84, wherein the substrate comprises steel.

[0160] Aspect 86. The substrate of aspect 84, wherein the substrate comprises aluminum.

[0161] Aspect 87. The substrate of aspect 83, wherein the substrate comprises composite.

[0162] Aspect 88. The substrate of aspect 83, wherein the substrate comprises a battery and / or a battery component.

[0163] Aspect 89. The substrate of aspect 88, wherein the battery comprises a lithium ion battery.

[0164] Aspect 90. The substrate of aspect 88, wherein the battery further comprises one or more fire-retardant materials and / or fire mitigation means inside and / or outside the battery.

[0165] Aspect 91. The substrate of aspect 83, wherein the substrate comprises a vehicle.

[0166] Aspect 92. The substrate of aspects 83 to 91, wherein the coating forms pail of a coating stack.

[0167] Aspect 93. The substrate of aspect 91, wherein the vehicle comprises a battery.

[0168] Aspect 94. The substrate of aspect 93, wherein the coating layer is between the vehicle and the battery.

[0169] Aspect 95. The substrate of aspect 94, wherein the battery or a component thereof is further coated according to the method of aspect 82.

[0170] The following Examples are intended to illustrate various aspects of the present invention and are not intended to limit the scope of the invention.ExamplesFormulation

[0171] Crosslinker I: A blocked polyisocyanate curing agent was prepared in the following manner. Components 2-6 were mixed in a flask set up for total reflux with stirring under nitrogen. The mixture was heated to a temperature of 30°C, and Component 1 was added slowly so that the temperature increased due to the reaction exotherm and was maintained below 110°C. After the addition of Component 1 was complete, Component 7 was added, and the reaction mixture was held at 110°C until no residual isocyanate was detected by IR spectroscopy. Components 8-9 were then added, and the reaction mixture was allowed to stir for 30 minutes to yield the product.Table 1. Preparation of Polyisocyanate curing agent (Crosslinker 1)’Available from Covestro as MONDUR MR, equivalent weight average 132 g / eq ant minimum isocyanate (NCO) content of 31.0%.2Available as MAZON 1651 from BASF.3DOWANOLPM, available from Dow Chemical Co.

[0172] Resin System I: An active hydrogen-containing, ionic salt group-containing filmforming polymer was prepared in the following manner. Components 1-4 were mixed in a flask set up for total reflux with stirring under nitrogen. The mixture was heated to a temperature of 130°C and allowed to exotherm (170°C maximum temperature). A temperature of 145°C was then established, and the reaction mixture was held for 1.5 hours. Component 5-7 was introduced slowly while allowing the mixture to cool to 100°C. Components 8-9 were added to the reaction mixture in rapid succession. The reaction mixture was allowed to exotherm, after which the mixture was held at 110°C for 1 hour. After the hold, the heating source was removed, and Component 10 was added affording resin synthesis product with a solids of 86.9%.Table 2, Preparation of Resin System I1Diglycidyl ether of bisphenol A with an epoxy equivalent weight of 186-190 g / eq, available from Westlake.2Available as MAZON 1651 from BASF.3D0WAN0L PM, available from Dow Chemical Co.

[0173] Resin System II: Resin System II was prepared according to the method described in EP2384358B1 with no modifications.Table 3. Preparation of Resin System II

[0174] Resin System III: An active hydrogen-containing, ionic salt group-containing film-forming polymer was prepared in the following manner. Components 1-5 were mixed in a flask set up for total reflux with stirring under nitrogen. The mixture was heated to a temperature of 130°C and allowed to exotherm (170°C maximum temperature). A temperature of 145°C was then established, and the reaction mixture was held for 1.5 hours. Components 6-8 were introduced slowly while allowing the mixture to cool to 100°C. Components 9-10 were added tothe reaction mixture in rapid succession. The reaction mixture was allowed to exotherm, after which the mixture was held at 110°C for 1 hour. After the hold, the heating source was removed, and Component 11 was added affording resin synthesis product with a solid of 88.0%.Table 4. Preparation of Resin System III

[0175] Preparation of Sulfonium Grind Vehicle: A typical sulfonium grind vehicle was made using the components listed in Table 5 and Table 6.Table 5. Preparation of Sulfonium quat mixtureTable 6. Preparation of Sulfonium Grind Vehicle

[0176] Preparation of Pigment Paste 1 : A stainless-steel beaker was loaded with the components described in Table 7. A 1.5-inch Cowles blade was used to agitate the mixture at 2500 RPM, powered by a Fawcett air motor (Model 103A), for thirty minutes. After mixing the material, the mixture was milled for 1 hour using an HM-l / 16th Micro Mill available from Hockmeyer Equipment Corporation.Table 7. Preparation of pre-mix and milling process1. Sulfonium grind vehicle made with components in Table 6.2. Titanium Dioxide available commercially from Tronox Inc.

[0177] Preparation of Pigment Paste 2: An aqueous bismuth solution was prepared using the ingredients from Table 8 in the following manner: Component 1 was added to an Erlcnmcycr flask with stirring, followed by the sequential introduction of Components 2 and 3. The content of the flask was stirred for 3 hours at room temperature, and the resulting catalyst solution was then filtered through a Buchner funnel to remove any undissolved residue.Table 8. Preparation of a Bismuth solution2. Bismuth trioxide commercially available from 5N Plus.

[0178] Next, Pigment Paste 2 was prepared by adding Zinc Oxide pigment to the bismuth solution, under mild agitation, using the weights described in Table 9. Once combined, the mixture was mixed for 3 hours using a 1.5-inch Cowles blade moving at 2000 RPM powered by a Fawcett air motor (Model 103A).Table 9. Preparation of Pigment Paste 21. Zinc Oxide powder commercially available from Sigma- AldrichELECTRODEPOSITABLE COATING COMPOSITIONS

[0179] Resin Dispersion I: A stainless-steel beaker (3 liter) was loaded with 1253.87 grams of Resin System I and warmed to 70°C using a thermocouple and heating mantle. A 1.5- inch-High lift blade was used to agitate the resin at 1200 RPM powered by a Fawcett air motor (Model 103A). The following ingredients were added in the order listed. To the resin was added 486.92 grams of Resin System II, which was allowed to incorporate for 5-10 minutes and mixed for 30 minutes. Next, 150 grams of deionized water was added slowly to the resin and mixed for ten minutes. In a separate stainless-steel beaker (1 liter), 46.27 grams of sulfamic acid was added to 562.95 grams of deionized water and mixed for half an hour under mild agitation. After the sulfamic acid was dissolved in the water, the solution was slowly poured into the resin mixture while continuing agitation. The acidified resin mixture was held for one hour at 60°C while continuing agitation. After the one-hour hold, the resin mixture was thinned with 1000 grams of deionized water for over 15 minutes, allowing the temperature to fluctuate naturally.Table 10. Components for the Preparation of Resin Dispersion I

[0180] Resin Dispersion II: A stainless-steel beaker (5 liters) was loaded with 2570.89 grams of Resin System III, which had been warmed to 70°C using a thermocouple and heating mantle. A 1.5-inch-High lift blade was used to agitate the resin at 1200 RPM powered by a Fawcett air motor (Model 103A). The following ingredients were added in the order listed. To the resin was added, 234.0 grams of deionized water was added slowly to the resin and mixed for ten minutes. In a separate stainless-steel beaker (1 liter), 67.97 grams of sulfamic acid wasadded to 999.06 grams of deionized water and mixed for half an hour under mild agitation. After the sulfamic acid was dissolved in the water, the solution was slowly poured into the resin mixture while continuing agitation. The acidified resin mixture was held for one hour at 60°C while continuing agitation. After the one-hour hold, the resin mixture was thinned with 1500 grams of deionized water for over 15 minutes, allowing the temperature to fluctuate naturally.Table 1 1 . Components for the Preparation of Resin Dispersion II

[0181] Resin Dispersion III: A stainless-steel beaker (3 liters) was loaded with 760.97 grams of Resin System I and warmed to 70°C using a thermocouple and heating mantle. A 1.5- inch-High lift blade was used to agitate the resin at 1200 RPM powered by a Fawcett air motor (Model 103A). The following ingredients were added in the order listed. To the resin was added 147.74 grams of Resin System II, which was allowed to incorporate for 5-10 minutes and mixed for 30 minutes. Next, 80 grams of deionized water was added slowly to the resin and mixed for ten minutes. In a separate stainless-steel beaker (1 liter), 24.13 grams of sulfamic acid was added to 320.50 grams of deionized water and mixed for half an hour under mild agitation. After the sulfamic acid was dissolved in the water, the solution was slowly poured into the resin mixture while continuing agitation. The acidified resin mixture was held for one hour at 60°C while continuing agitation. After the one-hour hold, the tin catalyst was introduced by adding 33.55 grams of E6278 (a dibutyl tin oxide [DBTO] paste available from PPG Industries) to provide a Sn loading of 0.72 weight % on resin solids, the resin mixture was thinned down with 766.66 grams of deionized water for over 15 minutes, allowing the temperature to fluctuate naturally.Table 12. Components for the Preparation of Resin Dispersion III

[0182] Pigmented composition 1: A stainless-steel beaker (3 liters) was loaded with 834.76 grams of Resin System I, which had been wanned to 70°C using a thermocouple and heating mantle. A 1.5-inch-High lift blade was used to agitate the resin at 1200 RPM powered by a Fawcett air motor (Model 103A). The following ingredients were added in the order listed. To the resin was added, 60 grams of deionized water was added slowly to the resin and mixed for ten minutes. Next, 152 grams of titanium dioxide was added to the resin over ten minutes. Next, 20 grams of deionized water was added dropwise along the beaker wall to rinse it. The milling process of titanium dioxide pigment commenced and maintained at 60°C. The process was continued until the Hegman fineness reading of 6+ was achieved. In a separate stainless- steel beaker (1 liter), 16.80 grams of sulfamic acid was added to 422.09 grams of deionized water and mixed for half an hour under mild agitation. After the sulfamic acid was dissolved in the water, the solution was slowly poured into the resin mixture while continuing agitation. The acidified resin mixture was held for one hour at 60°C while continuing agitation. After the one- hour hold, the tin catalyst was introduced by adding 33.55 grams of E6278 (a dibutyl tin oxide [DBTO] paste available from PPG Industries) to provide a Sn loading of 0.72 weight % on resin solids. Then the resin mixture was thinned with 755.6 grams of deionized water for over 15 minutes, allowing the temperature to fluctuate naturally. Afterward, 786 grams of deionized water was added to the dispersion to prepare an Electrocoat of 30% solids.Table 13. Components for the Preparation of Pigmented Composition I

[0183] Pigmented composition II: A stainless-steel beaker (3 liters) was loaded with 724.59 grams of Resin System 1 which had been warmed to 70°C using a thermocouple and heating mantle. A 1.5-inch-High lift blade was used to agitate the resin at 1200 RPM powered by a Fawcett air motor (Model 103A). To the resin was added 170.84 grams of Resin System II, which was allowed to mix for 5-10 minutes and mixed for 30 minutes. Next, 75 grams of deionized water was added slowly to the resin and mixed for ten minutes. In a separate stainless- steel beaker (1 liter), 18.78 grams of sulfamic acid was added to 251.79 grams of deionized water and mixed for half an hour under mild agitation. After the sulfamic acid was dissolved in the water, the solution was slowly poured into the resin mixture while continuing agitation. The acidified resin mixture was held for one hour at 60°C while continuing agitation. After the one- hour hold, the tin catalyst was introduced by adding 31.45 grams of E6278 (a dibutyl tin oxide [DBTO] paste available from PPG Industries) to provide a Sn loading of 0.72 weight % on resin solids. Then the resin mixture was thinned down with 248.2 grams of deionized water over 15 minutes, allowing the temperature to fluctuate naturally. Next, in the above resin dispersion, 561.2 grams of Pigment paste I, and 2295 grams of deionized water were added to create the electrocoat. The resulting bath was 20% solids.Table 14. Components for the Preparation of Pigmented Composition II

[0184] Pigmented composition III: In a 1 -gallon plastic bucket the following ingredients in the order listed, 551.03 grams of Resin Dispersion I, 337.5 grams of Pigment paste I, and 21.15 tin-catalyst by adding E6278 (a dibutyl tin oxide [DBTO] paste available from PPG Industries) (20.36 grams) to provide a Sn loading of 0.72 weight % on resin solids. Then the resin mixture was thinned down with 1290.32 grams of deionized water slowly poured into the mixture and mixed for an hour under mild agitation to create the final electrocoat. The resulting bath was 20% solids.Table 15. Components for the Preparation of Pigmented Composition III

[0185] Pigmented composition IV: To create this electrocoat, in a 1 -gallon plastic bucket the following ingredients in the order listed, 734.9 grams of Resin Dispersion II, 196.93 grams of Pigment paste I, and 92.34 grams of Pigment paste II. Then the resin mixture was thinned with 1175.83 grams of deionized water slowly poured into the mixture and mixed for an hour under mild agitation to create the final electrocoat. The resulting bath was 20% solids.Table 16. Components for the Preparation of Pigmented Composition IV

[0186] Pigmented composition V: This electrocoat was created by adding the following ingredients in the order listed in a 1 -gallon plastic bucket, 663.22 grams of Resin Dispersion II, 275.33 grams of Pigment paste I, and 86.76 grams of Pigment paste II. Then the resin mixture was thinned with 1174.7 grams of deionized water slowly poured into the mixture and mixed for an hour under mild agitation to create the final electrocoat. The resulting bath was 20% solids.Table 17. Components for the Preparation of Pigmented Composition V

[0187] Pigmented composition VI: An electrocoat was created by adding the following ingredients in the order listed in a 1-gallon plastic bucket, 536.86 grams of Resin Dispersion III, 371.53 grams of pigmented composition II, and 394.16 deionized water. This mixture was mixed for an hour under mild agitation. This resin mixture had 23% resin solids. Further, 507.99 grams of pigmented composition II, and 389.46 grams of deionized water were added into the mixture. Again, it was mixed for an hour under mild agitation to create the final electrocoat. The resulting bath was 20% solids.Table 18. Components for the Preparation of Pigmented Composition VI

[0188] Pigmented composition VTI: An electrocoat was created by adding the following ingredients in the order listed in a 1 -gallon plastic bucket, 687.97 grams of Pigmented Composition II, 2240.28 grams of pigmented composition VI. Then the resin mixture was thinned with 271.75 grams of deionized water slowly poured into the mixture and mixed for an hour under mild agitation to create the final electrocoat. The resulting bath was 20% solids.Table 19. Components for the Preparation of Pigmented Composition VIIEvaluation of Electrocoat Composition’s Resistance to High Temperature and Fire Exposure

[0189] Preparation of Coatings for High-Temperature Fire Exposure Testing: The pigmented composition I, II, II, IV, V, VI, and VII were used to electrodeposit coatings in duplicate over CRS panels pretreated with zinc phosphate (C700 / DI; item no. 28630 available from ACT, Hillsdale, MI.). Panels were cut in half, to a size of 4” by 6”. A rectifier (Xantrax Model XFR600-2, Elkhart, Indiana, or Sorensen XG 300-5.6, Ameteck, Berwyn, Pennsylvania) which was DC-power supplied was used. The panel was submerged in the electrocoat bath, which was under agitation. The rectifier was used to apply the electrical current to the clcctrocoat coating at specific bath temperatures. After the panels were clcctrocoatcd, they were rinsed with deionized water and baked at 350°F for 30 minutes in an electric oven (Despatch Model LFD-1-42). The target film build was 0.8 to 1 mil (20 to 25 microns). The exact deposition conditions for each run can be found in the table below.Table 20. Electrodeposition conditions

[0190] DIRECT FIRE EXPOSURE TEST: A flame chamber was built (3x4x5ft steel enclosure with a venturi exhaust providing airflow) using the Goss KP-320 torch (PA-I1-4-KP- 320) and an external propane tank (20 lbs). The chamber employed firebricks (Johns Manville, Super Firetemp® X), which are ceramic pieces made from ceramic blends of aluminosilicate calcium silicate capable of withstanding direct flames and extreme temperature changes while acting as heat insulators. Throughout the test, firebricks were used to securely hold the 4-inch by 6-inch electrocoated panels prepared as described above in place. These panels were adjusted and aligned with the torch, positioning the 4-inch edge of the sample 21 cm away from the torch. The 4-inch edge was perpendicular to the torch on the z-axis, while the 6-inch side of the sample was aligned with the torch’s line of sight. An Inconel heat shield was positioned between the torch and the panel. The propane tank pressure was set to 10 psi using a pressure regulator (Victor Edge 2.0 ESS32 Single-stage gas regulator). The torch drew in flammable propane gas, which combined indirectly with air and exited through a metal nozzle. The nozzle was ignited using a squeeze lighter to maintain a flame. The Inconel heat shield was removed. Once the flame encountered the 4-inch edge of the panel, a timer was started. After 10 seconds, the propane gas was shut off using a valve located outside the Flame chamber. The panel was then allowed to cool for 2 minutes before being removed from the Flame chamber for analysis.

[0191] A double solvent mb test was then performed on the panels to remove any loose burned film or char using the solvent mb resistance tester (QPI-SIRRT280 by Qualtech Products Industry). On the solvent mb resistance tester, the moving arm was moved all the way to the left and then the panels were mounted on the tester with the burned edge of the panels touching thecheesecloth (gauze) of the abrasive head mounted on the moving arm. Some isopropyl alcohol was dropped in the hole above the abrasive head and the upper part was installed. The test was run at a speed of 35 and a run cycle of 10. The solvent rub test was run to cover the panels from the edge of the burned part up to parts where the flame did reach. This solvent rub is part of the DIRECT FIRE EXPOSURE TEST.

[0192] FILM LOSS: The panels were then evaluated for film loss. A coating thickness gauge (Fischer Technology Inc. Dualscope FMP 40C) was used to find a complete film loss zone on the burned area. On the upper part of the panel where the solvent rub test was done, the probe was placed and dragged down until the reading showed zero or negative in microns. Once the point is found, we measure the length in mm from this point to the burned edge of the panel. The table below shows the result of this test. “Film loss” as used herein refers to use of this method following the DIRECT FIRE EXPOSURE TEST.Table 21. Complete film loss zone after DIRECT FIRE EXPOSURE TEST

Claims

What is claimed is:

1. A cationic fire-resistant electrodepositable coating composition comprising: a film-forming component; a hybrid organic-inorganic material, wherein the inorganic portion of the hybrid has an atom wt% of 0.20 or greater based on total solids weight of the composition and has a P:B of less than 0.20:1; and an inorganic pigment, wherein the inorganic pigment has an atom wt % of 8.0 wt% or greater based on total solids weight of the composition.

2. A cationic fire-resistant electrodepositable coating composition comprising: a film-forming component; a hybrid organic-inorganic material that is reactive with the film-forming component, wherein the inorganic portion of the hybrid has an atom wt% of 0.20 or greater based on total solids weight of the composition; and an inorganic pigment, wherein the inorganic pigment has an atom wt% of 8.0 wt% or greater based on total solids weight of the composition.

3. The cationic fire-resistant electrodepositable coating composition of any preceding claim, wherein the hybrid organic-inorganic material comprises a silicone resin, an organohalogen compound, an organophosphorus compound, a nano-gel, or a combination thereof.

4. The cationic fire-resistant electrodepositable coating composition of claim 3, wherein the organohalogen compound comprises chlorendic acid derivatives and chlorinated paraffins, dedecachloropentacyclooctadecadiene, organobromines such as decabromodiphenyl ether, decabromodiphenyl ethane, polymeric brominated compounds such as brominated polystyrenes, brominated carbonate oligomers, brominated epoxy oligomers, tetrabromophthalic anyhydride, tetrabromobisphenol A and hexabromocyclododecane, or a combination thereof.

5. The cationic fire-resistant electrodepositable coating composition of any of claim 3, wherein the organophosphorus compound comprises triphenyl phosphate (TPP), resorcinolbis(diphenylphosphate) (RDP), bisphenol A diphenyl phosphate (BADP), and tricresyl phosphate (TCP); phosphonatcs such as dimethyl mcthylphosphonatc (DMMP); and phosphinates such as aluminum diethyl phosphinate, or the fire-resistant pigment comprises both phosphorus and a halogen, such as tris(2,3-dibromopropyl) phosphate (brominated tris) and chlorinated organophosphates such as tris(l,3-dichloro-2-propyl)phosphate (chlorinated tris or TDCPP) and tetrakis(2-chlorethyl)dichloroisopentyldiphosphate (V6), or a combination thereof.

6. The cationic fire-resistant electrodepositable coating composition of claim 2, wherein the hybrid organic-inorganic material comprises a monomeric, oligomeric, or polymeric material comprising phosphorus that will react with functionality in the film-forming component, such as a phosphatized epoxy polymer, such as the reaction product of an epoxy resin and a phosphoric acid or ester thereof, which reaction can occur in the presence of an alcohol; P-H containing phosphine oxides including dimethylphosphine oxide (DMPO), diphenylphosphine oxide (DPPO), diphenyl phosphate (DPP), 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and derivates of any of these, and P-X containing phosphine or phosphine oxides, wherein X = halogen, such as Cl or Br, including phosphoryl chloride, phosphoryl bromide, phenyl dichlorophosphate (PDCP), diphenyl chlorophosphite (DPCP), 10-chloro-9,10-dihydro-9- oxa-10-phosphaphenanthrene (DOP-C1) and derivatives of any of these.

7. The cationic fire-resistant electrodepositable coating composition of any preceding claim, wherein the inorganic portion of the hybrid has and atom weight of 0.40 wt% or greater, or 0.50 wt% or greater, up to 5.0 wt% or lower, such as 4.0 wt% or lower, or 2.0 wt% or lower, or 0.20 to 5.0 wt% or 0.40 to 1.0 wt%, where atom weight percent is based on the total solids weight of the composition as determined by taking the mass fraction of the inorganic atoms in the hybrid mass, and determining what percentage that is of the total solids weight.

8. The cationic fire-resistant electrodepositable coating composition of any of the preceding claims, wherein the inorganic pigment has an atom wt% of 10 wt% or greater, or 20 wt% or lower, or 15 wt% or lower, or 8 to 20 wt% or 10 to 15 wt%, where weight percent is based on the total solids weight of the composition as determined by taking the weight fraction of the inorganic pigment in the total solids.

9. The cationic fire-resistant clcctrodcpositablc coating composition of claim 8, wherein the inorganic pigment comprises a metal hydroxide, such as aluminum hydroxide, aluminum oxide or a hydrate thereof, magnesium hydroxide, a zinc compound such as zinc borate or zinc hydroxystannate, a metal borate, titanium dioxide, barium sulfate, geopolymers such as alkali aluminosilicate, huntite, hydromagnesite, red phosphorus, boron compounds such as boric acid and borates, such as sodium borate, an organic layered silicate, wallastonite, carbonates such as calcium carbonate and magnesium carbonate, iron oxides, lead oxides, strontium chromate, barium sulfate, boron nitride, silicon nitride, aluminum nitride, boron arsenide, silicon dioxide, titanium oxide, zinc oxide, nickel oxide, copper oxide, tin oxide, silicon carbide, agate, emery, diamond, silver, zinc, copper, gold, carbonyl iron, copper, zinc, aluminum, clay, color pigments such as cadmium yellow, cadmium red, chromium yellow, or a combination thereof.

10. The cationic fire-resistant electrodepo sitable coating composition of any of the preceding claims, wherein the inorganic pigment comprises TiO2.

11. The cationic fire-resistant electrodepositable coating composition of claim 10, wherein the inorganic pigment further comprises a second inorganic pigment, such as zinc oxide and / or a clay pigment.

12. The cationic fire-resistant electrodepositable coating composition of any of the preceding claims, wherein the fire-resistant electrodepositable coating composition is substantially free, essentially free, or completely free of one or more of tin, bismuth, metal pigment, mica, aluminum oxide, inorganic glass particles, or melamine or a melamine derivative.

13. The cationic fire-resistant electrodepositable coating composition of any of the preceding claims, wherein the coating is an aqueous dispersion.

14. A coating layer deposited from the coating composition of any of claims 1-13, wherein the layer, when cured to a DFT of 0.8 to 1.0 mil passes the DIRECT FIRE EXPOSURE TEST.

15. A coating layer deposited from the coating composition of any of claims 1-13, wherein the layer, when cured to a DFT of 0.8 to 1.0 mil and tested under the DIRECT FIRE EXPOSURE TEST has a film loss or less than 7 mm, such as 6mm or less, or 2 mm or less.

16. A method of using the cationic fire-resistant electrodepositable coating composition of any of claims 1-13 to coat at least a portion of a substrate, comprising depositing such composition onto the substate using electrophoretic means.

17. A substrate coated according to the method of claim 16.

18. The coated substrate of claim 17, wherein the substrate comprises a battery and / or a battery component.

19. The coated substrate of claim 18, wherein the battery further comprises one or more fire- retardant materials and / or fire mitigation means inside and / or outside the battery.

20. The coated substrate of claim 17, wherein the substrate comprises a vehicle and the coating layer is part of a coating stack.

21. The coated substrate of claim 20, wherein the vehicle further comprises an electric battery and the coating layer is between the vehicle and the electric battery.

22. The coated substrate of claim 21, wherein at least a component of the electric battery has been coated according to the method of claim 16.

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