EP4739741A1 - Non-intumescent, protective coatings - Google Patents

Abstract

Non-intumescent coating compositions having a water generating material are disclosed, as are methods for using such compositions and substrates coated with same.

Description

NON-INTUMESCENT, PROTECTIVE COATINGS

FIELD

[0001] The present disclosure is directed to a non-intumescent, protective coating composition, to a method for using such composition to coat a substrate, to a substrate coated with said composition, and to an article comprising said substrate.

BACKGROUND

[0002] Protective coatings, such as fire-retardant coatings, have been used for a variety of structural applications to protect against both cellulosic and hydrocarbon fires. Such coatings offer protection by imparting 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 offshore 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. Such energy storage 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, are therefore desired.

SUMMARY

[0003] The present disclosure is directed to a coating composition comprising a) a filmforming component; and b) a water-generating material in an amount of 45 wt.% or greater based on total solids of the coating, wherein the coating is non-intumescent.

[0004] The compositions can be formed into a self-supporting film or sheet. Methods of using the coating composition and/or film or sheet to coat substrates, and substrates coated thereby, as well as articles comprising such coated substrates are also within the scope of the present disclosure.

BRIEF DESCRIPTION OF THE DRAWING

[0005] FIG. 1 is a schematic of the Thermal Runaway Test. DETAILED DESCRIPTION

[0006] The present disclosure is directed to a coating composition comprising a) a filmforming component; and b) a water-generating material in an amount of 45 wt.% or greater based on total solids of the coating, wherein the coating is non-intumescent.

[0007] The present coating composition can be used to form non-intumescent, protective coatings. “Protective coating” and like terms as used herein refer to a coating that passes the following test, shown in Figure 1 : the coating is applied to one side of a first steel panel 2 that is 0.6 to 1.2 mm thick and the coating is then cured to a dry film thickness of 2000 microns +/- 100 microns; a second steel panel 4, which may have the same thickness as the first steel panel 2, is placed on top of the cured coating 6 and the “sandwich” held together such that there are no gaps between the cured coating 6 and the two steel panels 2,4. The uncoated side 10 of the first steel panel 2 is exposed to 1450 ± 50°C at a thermal output of >5 kW; if, after five minutes exposure to the flame 8, the uncoated side 12 of the second steel panel 4 is at a temperature of 250°C or lower, such as when measured with a thermal couple 14, the coating is a protective coating within the scope of the present disclosure. Maintaining the uncoated surface of the second panel below this temperature demonstrates the thermally insulating properties of a coating. This test is intended to mimic a thermal runaway event in a battery and is therefore referred to herein as the “Thermal Runaway Test”. “Thermally insulating” and like terms refer to minimization of heat transfer between materials.

[0008] Coatings deposited from the present coating composition are non-intumescent. “Non-intumescent” and like terms, when used in reference to the present coatings, means that the coatings undergo expansion of no more than 5 times their dry film thickness upon exposure to 1450 ± 50°C at a thermal output of >5, such as below 3 times expansion, or below 1 time expansion. This expansion is significantly less than other coatings proposed for use with battery components, which may expand by 20 times or more of their dry film thickness. It is therefore a feature of the present disclosure to provide a composition with minimal expansion while still providing protection against fire.

[0009] The coating compositions according to the present disclosure are particularly suitable for the surfaces of energy storage devices, especially the inside surfaces of such devices. If applied to a battery used in an electric vehicle, the present coatings (or sheets/films made from the same) may contain excessive heat and/or fire within the battery and keep the heat/fire from spreading to other parts of the vehicle. The present coatings may retard, if not prevent, flammable materials in the car from catching fire. The thermal insulation of the present coatings may also mitigate heat damage outside of the energy storage device, such as damage to other parts of a vehicle or structure, and/or may mitigate the chance of igniting elements outside of the energy storage device.

[0010] 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, which terms may be used interchangeably. A 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 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”, “curing agent”, “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.

[0011] Any suitable resin or combination of resins can be used in the film-forming component, including, but not limited to, epoxy resins, acrylic resins, polysiloxane resins, polyurethane resins, polyurea resins, polyvinyl resins, phenolic resins, urea-formaldehyde resins, polyimide resins, melamine resins, polyester resins, and cyanate resins. Among these resins, epoxy resins, acrylic resins, and/or polyurethane resins are particularly suitable.

[0012] Film-forming resins used according to the present disclosure contain one or more functional groups that either react with each other or with the functional groups on the crosslinker. Examples of suitable functional groups include, for example, ketone, hydrazide, carbodiimide, oxazoline, epoxy, amine, vinyl, amide, carbamate, urea, mercaptan, carboxylic acid, (meth)acryloyl, isocyanate, alkoxysilyl, anhydride, hydroxyl, and alkoxy groups functional groups, and combinations thereof.

[0013] Suitable functional groups that are capable of reacting with each other include, for example, N-methylolamide groups; silane groups having silicon bonded hydrolysable or condensable groups, for example chloro, hydroxy, alkoxy, acetoxy and/or ketoximo groups; ethylenically unsaturated fatty acid groups such as those capable of oxidative drying; azomethine groups; azctidinc groups; and groups capable of thermally reversible Diels-Alder reaction, for example furan/maleimide. If the resin contains functional groups that are capable of reacting with each other, the resin is considered self-crosslinking, and the presence of a curing agent is not necessary in the present compositions.

[0014] The resin may also contain a combination of functional groups that are capable of reacting with each other (self-crosslinking) and functional groups that are reactive with the functional groups of the curing agent. In such cases, a curing agent may be present; upon cure, two crosslinking mechanisms will occur- the reaction between functional groups on the crosslinker and the resin and the self-crosslinking reaction of the resin itself.

[0015] Suitable epoxy resins for use in the present disclosure comprise at least one poly epoxide and have epoxy functionality. The poly epoxide typically has at least two 1,2-epoxy groups. The epoxy equivalent weight (grams of epoxy resin to give 1 mole of epoxy groups) of the polyepoxide may range from 80 to 6000, such as 100 to 700. Compounds comprising epoxy functionality can be saturated or unsaturated, cyclic, aliphatic, alicyclic, aromatic or heterocyclic. They may comprise substituent(s), such as halogen, hydroxy, and ether groups.

[0016] Examples of suitable polyepoxides are those having more than one or usually two 1,2-epoxy equivalents, i.e., polyepoxides having two epoxy groups per molecule on average. The most commonly used polyepoxides are, for example, polyglycidyl ether of polyphenols, such as 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), resorcinol, hydroquinone, benzenedimethanol, phloroglucinol, bisphenol F, and catechol; or polyglycidyl ether of polyols, such as alicyclic polyols, such as 1,2-cyclohexane diol, 1,4-cyclohexane diol, 2,2-bis(4- hydroxycyclohexyl)propane, 1 , 1 -bis(4-hydroxycyclohexyl)ethane, 2-methyl- 1 , 1 -bis(4- hydroxycyclohexyl)propane, 2,2-bis(4- hydroxy-3-tert-butylcyclohexyl)propane, 1,3- bis(hydroxymethyl)cyclohexane and l,2-bis(hydroxymethyl)cyclohexane. Examples of aliphatic polyols include, in particular, trihydroxymethylpentane diol, ethylene glycol, diethylene glycol, triethylene glycol, 1 ,2-propylene glycol, 1,4-butyleneglycol, 1,5-pentanediol, 1 ,2,6-hexanetriol, cyclohexanedimethanol, glycerol, trimethylolpropane, hydrogenated bisphenol A, hydrogenated bisphenol F or polyether glycols, for example, poly (oxy tetramethylene) glycol, poly(oxyethylene) glycol, poly(oxypropylene) glycol, and neopentane diol. [0017] Another group of suitable epoxy resins include polyglycidyl ethers of polycarboxylic acids, formed by the reaction of an epoxy compound such as epichlorohydrin with an aliphatic or aromatic polycarboxylic acid such as oxalic acid, succinic acid, glutaric acid, terephthalic acid, 2,6-napthalene dicarboxylic acid, or dimerised linoleic acid. Such resins are commercially available from Hexion Inc. in their EPIKOTE and EPON lines.

[0018] Other suitable epoxy resins that can be used according to the present disclosure comprise epoxidized olefinically unsaturated alicyclic materials such as epoxy alicyclic ethers and esters, epoxy resins containing oxyalkylene groups, epoxy novolac resins, which are prepared by reacting an epihalohydrin with the condensation product of an aldehyde with a monohydric or polyhydric phenol such as epoxy phenol novolac resins or epoxy cresol novolac resins.

[0019] Furthermore, it can be advantageous according to the present disclosure to employ a flexible polyepoxide resin as a polyepoxy-functional compound of the compositions of the present disclosure. “Flexible” resins are generally essentially linear materials, although some branching may be tolerated that imparts flexibility to the coating layer. Exemplary of suitable materials are epoxidized soybean oil, dimer acid-based materials such as EMPOL 1010 resin, which is commercially available from BASF SE, Ludwigshafen, Germany, and rubber-modified polyepoxide resins such as the product prepared from a polyglycidyl ether of bisphenol A and an acid-functional poly butadiene.

[0020] Other suitable examples of flexible polyepoxides for use according to the present disclosure include an epoxy-functional adduct, which is prepared from a flexible acid-functional polyester and polyepoxide. The acid-functional polyester can have an acid value of at least 10 mg KOH/g, such as 140 to 350 mg KOH/or 180 to 260 mg KOH/g, as determined by ASTM 974-87.

[0021] Linear polyesters may be more suitable than branched polyesters for use herein. Acid-functional polyesters can be prepared by the polyesterification of an organic polycarboxylic acid or anhydride thereof with an organic polyol. The polycarboxylic acids and polyols can be aliphatic or aromatic dibasic acids and diols.

[0022] The diols that may be used in making the polyester include alkylene glycols, such as ethylene glycol, diethylene glycol, neopentyl glycol, and other diols such as hydrogenated bisphenol A, cyclohexanediol, cyclohexanedimethanol, caprolactonediol, for example, the reaction product of epsilon-caprolactone and ethylene glycol, hydroxy-alkylated bisphenols, polycthcr glycols, for example, poly(oxytctramcthylcnc) glycol, poly(oxycthylcnc) glycol, poly(oxypropylene) glycol and the like. Polyols of higher functionality can also be used although diols may be more suitable. Examples include trimethylolpropane, trimethylolethane, pentaerythritol, glycerol, isosorbide, tetramethyl cyclobutane diol and the like, as well as higher molecular weight polyols such as those produced by oxyalkylating lower molecular weight polyols.

[0023] The acid component of the polyester may comprise monomeric dicarboxylic acids or anhydrides having 2 to 36 carbon atoms per molecule. Suitable acids include, for example, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, glutaric acid, chlorendic acid, tetrachlorophthalic acid, tetrabromophthalic acid, decanedioic acid, dodecanedioic acid, rosin acids, diphenolic acid, gallic acid, and other dicarboxylic acids of varying types, for example, Diels- Alder adducts of unsaturated Cis fatty acids.

[0024] The polyester may include minor amounts of monobasic acids such as benzoic acid, stearic acid, acetic acid, hydroxy stearic acid, and oleic acid. Also, there may be employed polycarboxylic acids having 3 or more acid groups, such as trimellitic acid. Where acids are referred to above, it is understood that anhydrides of those acids that form anhydrides can be used in place of the acid. Also, alkyl esters of the acids such as dimethyl glutarate and dimethyl terephthalate can be used.

[0025] According to the present disclosure, a polyester used to make the epoxyfunctional adduct may be prepared from a polycarboxylic acid component comprising a polycarboxylic acid or mixture of acids having from 7 to 16 carbon atoms and a polyol component comprising a portion of diethylene glycol.

[0026] The polyepoxides that may be used to prepare the epoxy -functional adduct of flexible acid-functional polyester and polyepoxide can be any of those described above for the polyepoxide-functional component according to the present disclosure.

[0027] Other suitable polyepoxy-functional compounds are epoxy-functional acrylic resins. Such resins can be prepared by free-radical addition polymerization of (meth)acrylic monomers, optionally in combination with vinyl monomers or other monomers comprising at least one carbon-carbon double bond, wherein the monomer composition comprises at least one cpoxy-functional compound having at least one carbon-carbon double bond.

[0028] Suitable epoxy-functional ethylenically unsaturated monomers include, for example, glycidyl (meth)acrylate, allyl glycidylether, vinyl glycidylether, vinyl cyclohexene oxide, limonene oxide, 2-ethylglycidylacrylate, 2-ethylglycidylmethacrylate, 2-(n- propyl)glycidylacrylate, 2-(n-propyl)glycidylmethacrylate, 2-(n-butyl)glycidylacrylate, 2-(n- butyl)glycidylmethacrylate, glycidylmethylmethacrylate, glycidylacrylate, (3',4'-epoxyheptyl)-2- ethylacrylate, (3',4'-epoxyheptyl)-2-ethylmethacrylate, (6',7'-epoxyheptyl)acrylate, (6', 7'- epoxyheptyl)methacrylate, allyl-3,4-epoxyheptylether, 6,7-epoxyheptylallylether, vinyl-3, 4- epoxyheptylether, 3,4-epoxyheptylvinylether, 6,7-epoxyheptylvinylether, o- vinylbenzylglycidylether, m-vinylbenzylglycidylether, p-vinylbenzylglycidylether, 3-vinyl cyclohexene oxide, alpha-methyl glycidyl methacrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate and combinations thereof.

[0029] Suitable additional monomers for the preparation of the epoxy-functional acrylic resin include, for example, ethylenically unsaturated nitrile compounds; vinyl aromatic monomers; alkyl esters of ethylenically unsaturated acids; hydroxy alkyl esters of ethylenically unsaturated acids; amides of ethylenically unsaturated acids; ethylenically unsaturated acids; ethylenically unsaturated sulfonic acid monomers and/or ethylenically unsaturated phosphorous- containing acid monomers; vinyl carboxylates; conjugated dienes; monomers having at least two ethylenically unsaturated groups; and combinations thereof.

[0030] Examples of ethylenically unsaturated nitrile monomers that can be used for the preparation of the epoxy-functional acrylic resin include polymerizable unsaturated aliphatic nitrile monomers that contain from 2 to 4 carbon atoms in a linear or branched arrangement, which may be substituted either by acetyl or additional nitrile groups. Such nitrile monomers include acrylonitrile, methacrylonitrile, alpha-cyanoethyl acrylonitrile, fumaronitrile and combinations thereof, with acrylonitrile being particularly suitable.

[0031] Representative suitable vinyl-aromatic monomers include, for example, styrene, oc-methylstyrene, p-methylstyrene, t-butylstyrene, and vinyltoluene.

[0032] Esters of (meth)acrylic acid that can be used for the preparation of the epoxyfunctional acrylic resin include n-alkyl esters, iso-alkyl esters or tert-alkyl esters of acrylic or (meth)acrylic acid in which the alkyl group has from 1 to 20 carbon atoms, the reaction product of methacrylic acid with glycidyl ester of a neoacid such as versatic acid, neodecanoic acid or pivalic acid and hydroxyalkyl (mcth)acrylatc and alkoxyalkyl (mcth)acrylatc monomers.

[0033] Suitable alkyl esters of (meth)acrylic acids may include, for example, C1-C20 alkyl (meth)acrylate, such as Ci-Cio-alkyl (meth)acrylates. Examples of such acrylate monomers include n-butyl acrylate, secondary butyl acrylate, methyl acrylate, ethyl acrylate, hexyl acrylate, tert-butyl acrylate, 2-ethyl-hexyl acrylate, isooctyl acrylate, 4-methyl-2-pentyl acrylate, 2- methylbutyl acrylate, methyl methacrylate, butyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate and cetyl methacrylate. Esters of (meth)acrylic acids, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and combinations thereof, are particularly suitable.

[0034] The hydroxy alkyl(meth)acrylate monomers that can be used for the preparation of the epoxy-functional acrylic resin include, for example, hydroxyalkyl acrylate and methacrylate monomers based on ethylene oxide, propylene oxide and higher (i.e., >3C) alkylene oxides or mixtures thereof. Examples are hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl acrylate. Particularly suitable is 2-hydroxy ethyl (meth)acrylate.

[0035] Amides of ethylenically unsaturated acids that can be used for the preparation of the epoxy-functional acrylic resin include, for example, acrylamide, methacrylamide, and diacetone acrylamide.

[0036] Vinyl ester monomers that can be used to prepare the epoxy-functional acrylic resin include vinyl acetate, vinyl proprionate, vinyl butyrate, vinyl benzoate, vinyl-2- ethylhexanoate, vinyl stearate, and the vinyl esters of versatic acid.

[0037] The ethylenically unsaturated carboxylic acid monomers suitable for the preparation of the epoxy-functional acrylic resin include, for example, monocarboxylic acid and dicarboxylic acid monomers and monoesters of dicarboxylic acid. Particularly suitable are ethylenically unsaturated aliphatic mono- or dicarboxylic acids or anhydrides that contain from 3 to 5 carbon atoms. Examples of monocarboxylic acid monomers include acrylic acid, methacrylic acid, crotonic acid and examples of dicarboxylic acid monomers include fumaric acid, itaconic acid, maleic acid and maleic anhydride. Examples of other suitable ethylenically unsaturated acids include vinyl acetic acid, vinyl lactic acid, vinyl sulfonic acid, 2-methyl-2- propene- 1 -sulfonic acid, styrene sulfonic acid, acrylamidomethyl propane sulfonic acid and the salts thereof. Suitable cthylcnically unsaturated carboxylic acid monomers include (mcth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid and combinations thereof.

[0038] Conjugated diene monomers suitable for the preparation of the epoxy-functional acrylic resin include 1,3-butadiene, isoprene, 2,3-dimethyl-l,3-butadiene, 2,3-dimethyl-l,3- butadiene, 2-chloro- 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, 1,3-octadiene, 2-methyl-l,3-pentadiene, 2, 3-dimethyl- 1,3-pentadiene, 3, 4-dimethyl- 1,3-hexadiene, 2,3-diethyl-

1.3-butadiene, 4, 5-diethyl- 1,3-octadiene, 3-butyl- 1,3-octadiene, 3,7-dimethyl-l,3,6-octatriene, 2- methyl-6-methylene-l,7-octadiene, 7- methyl-3-methylene-l,6-octadiene, 1,3,7-octatriene, 2- ethyl-1, 3-butadiene, 2-amyl- 1,3-butadiene, 3, 7-dimethyl- 1,3,7-octatriene, 3,7-dimethyl-l,3,6- octatriene, 3,7,11 -trimethyl- 1,3,6, 10-dodecatetraene, 7,1 l-dimethyl-3-methylene-l, 6,10- dodecatriene, 2,6-dimethyl-2,4,6-octatriene, 2-phenyl- 1,3-butadiene and 2-methyl-3-isopropyl-

1.3-butadiene and 1,3 -cyclohexadiene and combinations thereof.

[0039] It is also possible to use a combination of two or more, such as three or more or four or more, different polyepoxy-functional compounds in the film-forming component such as any of those disclosed above.

[0040] Suitable polyepoxy-functional compounds used according to the present disclosure may include diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, resorcinol diglycidyl ether, epoxy phenol novolac resin, epoxy cresol novolac resins, epoxy functional (poly)siloxanes, epoxy functional polysulfides, epoxy-functional adducts of acidfunctional polyesters and polyepoxides, for example, those that are described above. The acrylic resins used in the present disclosure may include, for example, copolymers of one or more alkyl esters of acrylic acid or methacrylic acid, optionally together with one or more other polymerizable ethylenically unsaturated monomers. Useful alkyl esters of acrylic acid or methacrylic acid include, for example, aliphatic alkyl esters containing from 1 to 30, such as 4 to 18, carbon atoms in the alkyl group. Examples include methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate, and 2-ethyl hexyl acrylate. Suitable other copolymerizable ethylenically unsaturated monomers include, for example, vinyl aromatic compounds such as styrene and vinyl toluene; nitriles such as acrylonitrile and 4- methacrylonitrile; vinyl and vinylidene halides such as vinyl chloride and vinylidene fluoride and vinyl esters such as vinyl acetate. [0041] The acrylic copolymers can include hydroxyl-functional groups, which are often incorporated into the polymer by including one or more hydroxyl-functional monomers in the reactants used to produce the copolymer. Useful hydroxyl-functional monomers include hydroxy alkyl acrylates and methacrylates, typically having 2 to 4 carbon atoms in the hydroxyalkyl group, such as hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, hydroxy-functional adducts of caprolactone and hydroxyalkyl acrylates, and corresponding methacrylates, as well as the beta-hydroxy ester-functional monomers described below. The acrylic polymer can also be prepared with N-(alkoxymethyl) acrylamides and N- (alkoxymethyl) methacrylamides.

[0042] Beta-hydroxy ester-functional monomers can be prepared from ethylenically unsaturated, epoxy-functional monomers and carboxylic acids having from 5 to 20 carbon atoms, or from ethylenically unsaturated acid-functional monomers and epoxy compounds containing at least 5 carbon atoms that are not polymerizable with the ethylenically unsaturated acid functional monomer.

[0043] The film forming resin used in the present disclosure can also comprise polyurethane. Among the polyurethanes that can be used are polymeric polyols that are prepared by reacting polyester polyols or acrylic polyols, such as those mentioned above, with a polyisocyanate such that the OH/NCO equivalent ratio is greater than 1:1 so that free hydroxyl groups are present in the product.

[0044] According to the present disclosure, the film-forming component can include combinations of epoxy resins and acrylic resins or epoxy resins and polyurethane resins, such as those disclosed in U.S. Pat. No. 5,108,832 or U.S. Pat. No. 5,070,119.

[0045] If the film-forming component comprises an epoxy resin and a polyamine and/or a polythiol-functional compound as a curing agent, as will be discussed below, the film-forming component may further comprise (i) a beta-hydroxy ester of (meth)acrylic acid; (ii) a (meth)acrylate-functional compound different from compound (i); or a combination thereof. [0046] The beta-hydroxy ester of (meth)acrylic acid may comprise a plurality of betahydroxy ester of (meth)acrylic ester groups resulting from the reaction of a polyepoxide with (meth)acrylic acid. The polyepoxide can be reacted with the (meth)acrylic acid in an epoxycarboxylic acid equivalent ratio of 1.0:0.1 to 1.0: 1.2, suitably 1.0:0.5 to 1.0: 1.2 more suitably 1.0: 1.0 to 1.0:1.05. A particularly suitable beta-hydroxy ester of (meth)acrylic acid is the reaction product of EPIKOTE 828 (reaction product of bisphenol A with epichlorohydrin) with acrylic acid, commercially available from Allncx as EBECRYL 3720.

[0047] The polyepoxides that can be used for the reaction product of polyepoxide with (meth)acrylic acid can be those polyepoxides as disclosed above.

[0048] In addition, or alternatively to the beta-hydroxy ester of (meth)acrylic acid (i), a (meth)acrylate-functional compound (ii) different from compound (i) may be present in the filmforming component. The viscosity of the composition of the present disclosure can be adjusted thereby. Thus, it is believed that the optional component (ii) functions as a reactive diluent. The optional (meth)acrylate-functional component (ii) of the present compositions may include, for example, poly(meth)acrylates of 1 ,4-butanediol, neopentyl glycol, ethylene glycol, 1,2- propanediol, 1,3-propanediol, 2,2,4-trimethyl-l,3-pentanediol, 1,6-hexanediol, 1,4-cyclohexane dimethanol, para- xylene glycol, 1,4-cyclohexane diol, trimethylolethane, trimethylolpropane, pentaerythritol, polyether glycols, for example, poly(oxytetramethylene) glycol, poly(oxyethylene) glycol, poly(oxypropylene) glycol and combinations thereof.

[0049] As noted above, the film-forming component may also comprise a crosslinker. Any suitable crosslinker can be used according to the present disclosure and will be chosen by one skilled in the art to react with the functional groups of the film-forming resin. Suitable crosslinkers include, for example, polyamines, for example polyetheramines, polyamides, polyepoxides, aminoplast resins, phenolic resins, polyisocyanates, polythiols, and polyols, etc. [0050] The curing agent may also be a latent or blocked curing agent, wherein the actual functional group that is reactive with the functional groups of the film-forming resin is generated or restored in a deblocking reaction at curing conditions such as elevated temperatures. Suitable curing agents of said type are, for example, blocked polyisocyanates. Thus, the term polyisocyanate as used herein encompasses blocked and free polyisocyanates. Latent or blocked curing agents are particularly suitable to provide single component compositions to secure sufficient storage stability and pot life prior to application and curing.

[0051] The polyamine curing agent can include, for example, aliphatic polyamines, aromatic polyamines, polyamine amides, polyetheramines, for example those commercially available from Huntsman Cooperation, The Woodlands, Texas, polysiloxane amines, polysulfide amines or combinations thereof. Examples include diethylene triamine, 3,3-amino-bis- propylamine, triethylene tetraamine, tetraethylene pentamine, m-xylylenediamine, isophorone diamine, l ,3-bis(aminoethyl)cyclohexane, bis(4-aminocyclohexyl)methane, N-aminoethyl piperazine, 4,4’-diaminodiphcnyl methane, 4,4’-diamino-3,3’-dicthyl diphenyl methane and diamino diphenylsulphone and the reaction product of a polyamine and an aliphatic fatty acid such as the series of materials sold by BASF under the trademark VERSAMID, which are particularly suitable.

[0052] In addition, adducts of any of the above polyamines can also be used. The adduct of polyamine is formed by reacting polyamine with a suitable reactive compound, such as an epoxy resin. This reaction will decrease the content of free amine in the curing agent, making it more useful at low temperature and/or high humidity environment.

[0053] As a curing agent, various poly etheramines, such as various JEFFAMINES available from Huntsman Corp., including, but not limited to, JEFF AMINE D-230, JEFF AMINE D-400, JEFFAMINE 600, JEFF AMINE 1000, JEFF AMINE 2005 and JEFFAMINE 2070, etc., can also be used.

[0054] As a curing agent, various polyamides can also be used. Generally, polyamides contain reaction products of dimer fatty acid and polyethyleneamine, and small amounts of monomer fatty acid. Dimer fatty acid is prepared by the oligomerization of monomer fatty acid. Polyethyleneamine can be any higher polyethyleneamine, such as diethylenetriamine, triethylenetetraamine, tetraethylenepentaamine, etc., wherein the most commonly used is diethylenetriamine. When polyamides are used as the curing agent, it may impart one or more desirable properties to the coating, such as corrosion resistance, water resistance, and/or good flexibility.

[0055] The polythiol compounds useful as curing agents may include polysulfide thiols, polyether thiols, polyester thiols, pentaerythritol based thiols, or combinations thereof. A particularly suitable polythiol compound is THIOPLAST G4, commercially available from Akzo Nobel Functional Chemicals GmbH&Co KG, Greiz, Germany.

[0056] As mentioned above, if the film-forming resin comprises an epoxy resin, a polyamine, a polythiol compound, or a combination thereof may be used as a crosslinker.

[0057] In the coating composition of the present disclosure, the equivalent ratio of the combined functional groups in the film-forming resin, such as epoxy groups if an epoxy resin is used, to the functional groups in the curing agent may be from 2:1 to 1:2, such as from 1.05:1.00 to 1:2, or from 1.0: 1.4 to 1 :2. [0058] The coating composition may comprise the film-forming component in any suitable amount. For example, the coating composition may contain 10 wt.% or greater of the film-forming component, such as 30 wt.% or greater or 40 wt. % or greater. The coating composition may for example contain 50 wt.% or less of the film-forming component, such as 40 wt. % or less or 20 wt. % or less. The coating composition can, for example, comprise the filmforming component in an amount in a range of any of the above-mentioned values such as from 10 wt. % to 50 wt. %, from 15 wt. % to 40 wt. % or from 20 wt. % to 50 wt. %. Wt. % as reported herein is based on total solid weight of the composition unless indicated otherwise. [0059] The compositions of the present disclosure further comprise a water-generating material. “Water-generating material” and like terms as used herein refer to materials that release water when heated to 100°C or greater, such as hydrated metal oxides, including A1(OH)3 (“ATH”), Mg(OH)2, and Ca(OH)2. The coating composition may comprise the water-generating material in an amount of 45 wt. % or greater, such as 50 wt.% or greater, 55 wt.% or greater, or 60 wt.% or greater. The coating composition may comprise the water-generating material in an amount of 70 wt.% or less, such as 65 wt.% or less, or 60 wt.% or less. The amount of watergenerating material may range from 45 to 70 wt.%, such as 50 to 65 wt.% or 50 to 60 wt.%. If the amount of water-generating material is too low (i.e., less than 45 wt.%), it may not adequately protect the substrate to which the coating is applied and if it is too high (i.e., greater than 70 wt.%) viscosity might make application too difficult.

[0060] The coating compositions of the present disclosure may further comprise a phosphate source. “Phosphate source” as used herein means any phosphorus-containing material that comprises phosphoric acid or condensation or dehydration products (including oxides) thereof, or salts, esters, amides or other derivatives of any of the foregoing. The phosphate source can comprise a variety of materials, such as, for example, phosphoric acid, mono- and diammonium phosphate, triphenyl phosphate, tris-(2-chloroethyl)phosphate, tri(2- chloroisopropyl)phosphate, phosphorus-containing amides such as phosphorylamide, and melamine pyrophosphate. Suitably, the source of phosphorous is an ammonium polyphosphate represented by the formula (NH4)n+2 PnChn+i, wherein n is an integer of at least 2, such as at least 50. The composition of the present disclosure may contain the phosphate source in an amount of 15 wt. % or greater, such as 20 wt. % or greater, 25 wt. % or greater, or 30 wt. % or greater, 35 wt.% or greater, or 40 wt.% or greater. The coating composition may comprise the phosphate source in an amount of 50 wt. % or less, such as 45 wt. % or less, or 40 wt. % or less, or 35 wt. % or less. The coating composition may comprise the phosphate source in an amount in a range of the above-mentioned values such as from 15 to 50 wt. %, for example, from 20 to 40 wt. %, or from 15 to 35 wt. %. The wt. % reported herein are based on the total solid weight of the composition. The phosphorous is believed to function as a char promoter in the present composition.

[0061] The coatings of the present disclosure may contain one or more additional additives suitable for use in fire retardant coatings. Examples of such additives include a borate source, a silica source, a zinc source, an acid source, a metal oxide, for example pre-hydrolysed tetraethylorthosilicate, titanium isopropoxide, a carbon source, inorganic fillers, glass fibers and/or mineral fibers, for example CHOPVANTAGE from PPG, Coatforce or Roxul fibers from Lapinus, rheology additives, organic solvents, pigments, foam stabilizers, and combinations thereof.

[0062] Borate source” as used herein means any boron-containing material that contains boric acid, or condensation or dehydration products (including oxides) thereof, or salts or esters of any of the foregoing. Suitable borate sources include, for example, ammonium pentaborate, boric acid, metal borates such as zinc borate, boron oxide, borates such as sodium borate, potassium borate, and ammonium borate, borate esters such as butyl borates or phenyl borates, and combinations thereof. “Silica source” as used herein means any silicon-containing material that contains polysiloxane, silane, silicic acid, condensation or dehydration products (including oxides) thereof or salts or esters of any of the foregoing. Suitable silica sources include fumed silica or quartz, such as those having a particle size below 150 pm, or a substance that contains silica such as bentone or kaolin.

[0063] The borate source, if used, may be used in any suitable amount, in an amount of 5 wt.% or greater, such as 6 wt.% or greater, such as 7 wt.% or greater, such as 8 wt.% or greater, such as 9 wt.% or greater, such as 10 wt.% or greater. The coating composition may comprise the borate source in an amount of 20 wt.% or less, such as 19 wt.% or less, or 18 wt.% or less, or 15 wt.% or less. The coating composition may comprise the borate source in an amount in a range of the above-mentioned values such as from 5wt.% to 20 wt.%, or from 6 wt.% to 15 wt.%, or from 9 wt.% to 15 wt.%. The compositions of the present disclosure may contain a silica source in any suitable amount, such as an amount of 0.1 wt.% or greater, such as 0.2 wt.% or greater, or 0.3 wt.% or greater, or 0.4 wt.% or greater, or 0.5 wt.% or greater. The coating composition may comprise the silica source in an amount of 5 wt.% or less, such as 3 wt.% or less, or 2 wt.% or less, or 1 wt.% or less, or 0.8 wt.% or less. The composition may comprise the silica source in an amount in a range of the above-mentioned values such as from 0.1 to 5 wt. %, or from 0.4 to 1 wt. %. The wt. % reported above are each based on the total solid weight of the composition.

[0064] The optional source of zinc can comprise a variety of materials. It is believed that the zinc material may contribute to the formation of a small-celled structure in the chai'. The small cells of the char may provide better insulation of the substrate and are better able to retain the char's integrity and adhere to the substrate. Thus, cracking of the char and its breaking away from the substrate are minimized and a greater measure of protection is afforded to the underlying substrate. Examples of suitable materials that are sources of zinc include zinc oxide, zinc salts, such as zinc borate and zinc phosphate, zinc carbonate, zinc metal, and combinations thereof.

[0065] The acid source may comprise ammonium phosphate, ammonium polyphosphate, diammonium diphosphate, diammonium pentaborate, phosphoric acid-generating materials, boric acid, metal or organic borates and combinations thereof.

[0066] It should be understood that many of the components of the present composition may serve more than one function in the composition. That is, a single material may be a source of more than one of the recited components of the composition. For example, zinc borate can provide a source of zinc and a source of borate; zinc phosphate may provide a source of zinc and a source of phosphate, and the like. The amount of zinc in zinc borate should be considered in the total amount of zinc in the composition and likewise the amount of borate in the total amount of borate source.

[0067] The optional reinforcing fillers may be chosen from among a large array of conventionally utilized materials, including fibrous reinforcements and platelet reinforcements, which may be suitable over other fillers. Examples of fibrous reinforcements include glass fibers, ceramic fibers, e.g., aluminum oxide/silicon oxide, graphite fibers, mineral fibers and basalt fibers. Platelet reinforcements include hammer-mill glass flakes, mica, and wollastonite. Other suitable fillers include metal oxides, clay, talc, silica, diatomaceous earth, LAPINUS fibers and various pigments. When present, the reinforcing filler, such as glass fibers and/or mineral fibers, is usually present in the composition in an amount of 5.0 wt.-% or less, such as 4.0 wt.% or less, such as 3.0 wt.% or less, based on the total solid weight of the composition. The composition according to the present disclosure can for example comprise the reinforcing filler in an amount of 0.1 wt.% or greater, such as 0.2 wt.% or greater, 0.5 wt.% or greater, or 1.0 wt.% or greater. The composition may comprise the reinforcing filler in an amount in a range of the above-mentioned values such as from 0.1 wt.% to 5.0 wt.% or from 1.0 wt.% to 4.0 wt.%. The wt.% reported are each based on the total solid weight of the composition.

[0068] The compositions of the present disclosure may also contain a variety of conventional additives, such as rheology additives, organic solvents, foam stabilizers, pigments, and the like. These ingredients are optional and can be added in varying amounts. Typically, if additional additives are used, they are present in a total amount of 1 wt.% or greater, such as 2 wt.% or greater, or 5 wt.% or greater, or 10 wt.% or greater. The additional additives, if used, can for example be present in the compositions according to the present disclosure in an amount of 20 wt.% or less, such as 15 wt.% or less, or 12 wt.% or less. The composition may comprise the optional additional additives in an amount in a range of the above-mentioned values such as from 1 to 20 wt.%, such as 2 to 20 wt.% or 5 to 15 wt.%. The wt.% reported are each based on total solid weight of the composition.

[0069] It might also be desirable that the coating compositions of the present disclosure specifically exclude certain chemicals or components. For example, the present compositions may be substantially free, essentially free, or completely free of one or more of the following: a borate source, alkyl phosphorus acid(s), melamine or melamine derivatives (compounds that are the reaction product of melamine and another compound), residues of ethylenically unsaturated monomers such as those from (meth)acrylic acid and/or styrene, a surfactant including a nonionic surfactant, silicates including layered silicate, and aluminum silicate(s), and piperazine salt(s), reinforcing fillers as listed above, such as fibers, and solvent. “Substantially free” as used in this context means the composition comprises 2.0 wt. % or less of any of these compounds, “essentially free” means 1.0 wt. % or less of any of the compounds, and “completely free” means that the compounds contain, if any, only trace amounts such as would be present as an impurity in another compound. The wt.% reported are each based on total solid weight of the composition. “Residues of ethylenically unsaturated monomers” refers to the portion of an ethylenically unstaturated monomer that remains after reaction of the film-forming component. [0070] Because the coating compositions of the present disclosure are non-intumescent, they may also be free of compounds that will cause the coating to expand to more than 5 times its dry film thickness. For example, gas generating compounds such as melamine may be excluded from the present compositions. It will be appreciated that very minor amounts of these materials may be present and result in some expansion upon heating, but that is not an intended result of the present coatings. The water-generating material may cause some expansion of the heated coating due to vaporization of the water released, but again this minimal expansion is within the scope of a “non-intumescent” coating as defined.

[0071] The present compositions may be either one component (“IK”), or multicomponent compositions such as two component (“2K”) or more. A IK composition will be understood as referring to a composition wherein all the coating components arc maintained in the same container after manufacture, during storage, etc. A IK composition can be applied to a substrate and cured by any conventional means, such as by heating, forced air, and the like. The present compositions can also be multi-component, which will be understood as compositions in which various components are maintained separately until just prior to application. The present compositions can be thermoplastic or thermosetting. For example, the present compositions might be packaged as a 2K system, with the film-forming resin in a first package (A) and a curing agent therefor in a second package (B), whereby all of the other components used in the coating composition are used in any combination in either package (A) or package (B) or in both, or some or all may be in one or more further packages (C). That is, the water-generating material can be in both the film forming resin component and the curing agent component. Indeed, to achieve the high levels of water-generating material claimed in the present disclosure, it may be necessary to divide the amount into each of the components. The individual packages are mixed prior to use of the composition.

[0072] The coating composition of the present disclosure may be in the form of a viscose material such as a mastic. It is particularly suitable that the composition be free of organic solvent and spray-applied. If desired, thinning can be accomplished with a variety of conventional solvents such as xylene, methylene chloride, or 1,1,1 -trichloroethane.

[0073] The coating composition of the present disclosure may be applied to provide the various dry film thicknesses as desired. Suitable dry film thicknesses can range from 10 - 20,000 microns, such as 50 - 5000 microns, such as 100 - 2000 microns. The desired dry film thickness (“DFT”) can vary depending on the application. For use on energy storage devices, such as lithium batteries, a DFT ranging from 200 to 5000 microns, such as 200 to 3000, such as 2000 +/- 100, may be suitable. It will be appreciated that there is often limited space within a battery pack, and so a smaller DFT might be particularly suitable.

[0074] Alternatively, the compositions of the present disclosure can be formed into a self-supported film or sheet. The self-supported film or sheet may subsequently be cured to form a crosslinked non-intumescent self- supported film or sheet. In general, the curable compositions of the present disclosure can be formed into a film or sheet by any technique well known to a person skilled in the art, for example a cast-molding process, by impregnating a mesh with the coating, and the like. The film or sheet can be cured to form a crosslinked self- supported film or sheet that can then be applied to a substrate. It is also within the present disclosure that after the forming step the uncured film or sheet is applied to a substrate and then subsequently cured to obtain the coating layer according to the present disclosure. The film or sheet may be applied to the substrate through an adhesive. Accordingly, when reference is made herein to a substrate being “coated with”, or like terms of the present compositions, this includes coating by application of a film and/or sheet formed from the compositions(s).

[0075] The present compositions and self-supporting sheets or films can be applied to any substrates known in the art, for example, automotive substrates, marine substrates, industrial substrates, heavy-duty equipment, packaging substrates, lumber, wood flooring and furniture, apparel, 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, and the like, glass and transparencies, sports equipment and the like. These substrates can be, for example, metallic or non-metallic. Metallic substrates include 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”), polycarbonate, polycarbonate aery lob utadiene styrene (“PC/ABS”), SMC, carbon fiber, polyamide, wood, veneer, wood composite, particle board, medium density fiberboard, cement, stone, glass, paper, cardboard, textiles, leather both synthetic and natural, and the like. The substrate can be part of a structure or pail of a vehicle. “Structure” as used herein refers to any pail of a building, bridge, transportation infrastructure, oil rig, oil platform, water tower, power line tower, support structure, wind turbine, wall, pier, dock, levee, dam, shipping container, trailer, and any metal structure that is exposed to a corrosive environment. “Vehicle” as used herein refers to in its broadest sense all types of vehicles, such as but not limited to 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.

[0076] The substrate can be one that has been already treated in some manner, such as to impart visual and/or color effect. For instance, the substrate can be alkaline cleaned, deoxidized, mechanically cleaned, ultrasonically cleaned, solvent wiped, roughened, plasma cleaned or etched, exposed to chemical vapor deposition, treated with an adhesion promoter, plated, anodized, annealed, cladded, or any combination thereof prior to application of the coating composition. The substrate can be treated using any of the previously described methods prior to application of the coating composition such as by dipping the substrate in a cleaner and/or deoxidizer bath prior to applying the coating composition. The substrate can also be plated prior to applying the coating composition. As used herein, “plating” refers to depositing a metal over a surface of the substrate. The substrate may also be 3D printed.

[0077] As discussed above, 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. [0078] Accordingly, the present disclosure is further directed to an article coated at least in part with a coating composition of the present disclosure, such as an article that comprises any of the above substrates. The coating composition of the present disclosure can be applied to an article in any form, such as a coating composition or a self-supported film or sheet. “Applied to” and any variants thereof when referring to the film or sheet means that the film/sheet can be affixed to an article, such as by means of an adhesive layer, or positioned within or placed within an article, such as adjacent to a fixed or movable member of the article. The article can be a structure. The article can be a vehicle. The article can be a battery component or a battery, such as a lithium-ion battery or other energy storage device. For example, the coating composition of the present disclosure or the crosslinked self- supported film or sheet can be applied to any structural element of a battery, in particular a lithium-ion battery, to obtain a battery according to the present disclosure. The battery may comprise exterior wall elements defining a housing and optionally interior wall elements, wherein the coating or self-supported film or sheet is at least partially applied to the external and/or internal side of any of the exterior wall elements and/or to any side of any of the interior wall elements, if present. The exterior wall and/or interior wall elements may comprise composite, steel, aluminum and/or polycarbonate for example. The present coating compositions may be particularly suitable for use on the inside of a battery or other energy storage device, where space for a coating layer or film may be limited. This can prevent or at least minimize the likelihood of overheating of the substrate during a thermal runaway event.

[0079] The battery, in particular a lithium-ion battery, may include a battery pack comprising a plurality of individual battery cells, wherein the present coating or the crosslinked self-supported film or sheet is positioned to thermally insulate at least some of the individual battery cells from each other in the expanded and optionally charred state, such as in between two battery cells. In addition, the coating composition or self-supported film or sheet may be applied to or placed adjacent to the housing walls and interior dividing walls of the battery pack as discussed above.

[0080] 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, calciumsilicate, 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.

[0081] To provide fire protection for articles comprising a battery and their users it is also within the present disclosure to apply the curable coating composition or the crosslinked self-supported film or sheet 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. 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, or a laptop computer.

[0082] Alternatively, the article may be a vehicle such as a hybrid or electric car, bus or truck. In such vehicles it is common to position the battery, especially the lithium-ion battery due to its weight, as a flat battery pack underneath the floor portion of the vehicle body, for example the car body. In such cases, the coatings of the present disclosure including a selfsupported film or sheet may be applied to the floor portion of the vehicle adjacent to the battery between the battery and the vehicle body. In an event of a thermal runaway of the battery or a battery fire, the car body, especially the passenger cabin, would be protected by the coating layer/film/sheet of the present disclosure so that the battery box will resist flame and any fire inside the battery box will not spread into the passenger cabin and the heat-up of the passenger cabin would be limited for a prolonged period of time so that the passengers can safely escape from the vehicle in case of such an incident.

[0083] It may also be desirable to apply to the vehicle, particularly the area in contact with or adjacent to the battery, a fire-resistant ecoat coating. “Fire-resistant ecoat” as used herein refers to an ecoat layer that has been deposited from an electrodepositable composition comprising a fire-retardant pigment, an inorganic, platelike pigment, such as a phyllosilicate pigment, and/or having a pigment-to-binder (P:B) ratio of 0.4: 1.0 or higher, such as 0.5: 1.0 all the way up to 2.0: 1.0. These coatings, due to their use of a fire-retardant pigment or high pigment content, may be less likely to be combustible as compared to electrodepositable coatings having a lower pigment content. Suitable examples include those disclosed in U.S. Pat. No. 10,697,081; U.S. Pub. No. 2023/044601 Al, IntT Pub. No. 2021/127327A1; and IntT Pub. No. 2022/133202 Al. Flame -retardant adhesives, such as those formulated as sealants, gap fillers, pottants, and encapsulants, can also be used, including those formed from a composition comprising a flame retardant. As used herein, “flame retardant” refers to a material that slows down or stops the spread of fire or reduces its intensity. Flame retardants may be available as a powder that may be mixed with a composition, a foam, or a gel that may form a coating on a substrate surface and such coating may function as a flame retardant. Suitable examples include those disclosed in Int’l Publ. No. 2021211722A1, pars. 57-309; Int’l Publ. No. 2021211183A1, pars. 44-178; Int’l Publ. No. 2021211184A1, pars. 52-252; Int’l Publ. No. 2021211694A1, pars. 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.

[0084] The compositions of the present disclosure can be applied by any means standard in the art, such as electrocoating, spraying, electrostatic spraying, dipping rolling, brushing, and the like, including application robotically. Application can be by precision spraying, in which the composition is sprayed to a specific portion of the substrate without overspray.

[0085] 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” water generating material, 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 C1-C6 alkyl esters and hydroxy alkyl esters, unless clearly indicated otherwise. [0086] Aspects of the invention include:

[0087] Aspect 1. A coating composition comprising: a) a film forming component; and b) a water-generating material in an amount of 45 wt.% or greater based on total solids of the coating, wherein the coating is non-intumescent.

[0088] Aspect 2. The coating composition of Aspect 1, wherein the water generating material is present in an amount of 50 wt.% or greater.

[0089] Aspect 3. The coating composition of Aspect 1, wherein the water generating material is present in an amount of 55 wt. % or greater

[0090] Aspect 4. The coating composition of Aspect 1, wherein the water generating material is present in an amount of 60 wt.% or greater

[0091] Aspect 5. The coating composition of any preceding aspect, wherein the water generating material is present in an amount of 70 wt.% or less.

[0092] Aspect 6. The coating composition of any preceding aspect, wherein the water generating material is present in an amount of 65 wt.% or less.

[0093] Aspect 7. The coating composition of any preceding aspect, wherein the water generating material is present in an amount of 60 wt.% or less.

[0094] Aspect 8. The coating composition of any preceding aspect, wherein the water generating material is present in an amount of 45 to 70 wt.%.

[0095] Aspect 9. The coating composition of any preceding aspect, wherein the water generating material is present in an amount of 50 to 65 wt.%.

[0096] Aspect 10. The coating composition of any preceding aspect, wherein the water generating material is present in an amount of 50 to 60 wt.%.

[0097] Aspect 11. The coating composition of any preceding aspect, further comprising a borate source.

[0098] Aspect 12. The coating composition of any preceding aspect, further comprising a silica source.

[0099] Aspect 13. The coating composition of any preceding aspect, further comprising a zinc source.

[00100] Aspect 14. The coating composition of any preceding aspect, further comprising an acid source. [00101] Aspect 15. The coating composition of any preceding aspect, further comprising a metal oxide that is not a water-generating material.

[00102] Aspect 16. The coating composition of any preceding aspect, further comprising titanium isopropoxide.

[00103] Aspect 17. The coating composition of any preceding aspect, further comprising a carbon source.

[00104] Aspect 18. The coating composition of any preceding aspect, further comprising inorganic fillers.

[00105] Aspect 19. The coating composition of any preceding aspect, further comprising glass fibers and/or mineral fibers.

[00106] Aspect 20. The coating composition of any preceding aspect, further comprising rheology additives.

[00107] Aspect 21. The coating composition of any preceding aspect, further comprising organic solvents.

[00108] Aspect 22. The coating composition of any preceding aspect, further comprising pigments.

[00109] Aspect 23. The coating composition of any preceding aspect, further comprising foam stabilizers.

[00110] Aspect 24. The coating composition of any of Aspect 11-23, comprising one or more additives of these additives in a total amount of 2-20 wt. %, where wt.% is based on the total solid weight of the composition.

[00111] Aspect 25. The coating composition of any preceding aspect in which the filmforming component comprises an epoxy resin and amine crosslinker, and the water-generating material comprises a hydrated metal oxide.

[00112] Aspect 26. The composition of any preceding aspect, wherein the composition is substantially free, essentially free, and/or completely free of a borate source.

[00113] Aspect 27. The composition of any preceding aspect, wherein the composition is substantially free, essentially free, and/or completely free of alkyl phosphorus acid(s).

[00114] Aspect 28. The composition of any preceding aspect, wherein the composition is substantially free, essentially free, and/or completely free of melamine or melamine derivatives. [00115] Aspect 29. The composition of any preceding aspect, wherein the composition is substantially free, essentially free, and/or completely free of the residue of cthylcnically unsaturated monomers, such as those from (meth) acrylate and/or styrene.

[00116] Aspect 30. The composition of any preceding aspect, wherein the composition is substantially free, essentially free, and/or completely free of a surfactant, such as a non-ionic surfactant.

[00117] Aspect 31. The composition of any preceding aspect, wherein the composition is substantially free, essentially free, and/or completely free of silicate, such as layered silicate, and/or aluminum silicate.

[00118] Aspect 32. The composition of any preceding aspect, wherein the composition is substantially free, essentially free, and/or completely free of piperazine salt.

[00119] Aspect 33. The composition of any preceding aspect, wherein the composition is substantially free, essentially free, and/or completely free of a reinforcing filler, such as fibers, and/or a solvent.

[00120] Aspect 34. A self- supported film or sheet formed from the coating composition of any preceding aspect.

[00121] Aspect 35. The coating layer deposited from the coating composition of any of Aspects 1-33 or self-supported film or sheet of Aspect 34 where the coating/film/sheet is a protective coating as determined according to the Thermal Runaway Test.

[00122] Aspect 36. A method for using the coating composition, film, or sheet of any preceding aspect to coat a substrate comprising applying to at least a portion of the substrate, the coating composition or the film or sheet of any of Aspects 1-35.

[00123] Aspect 37. The method of Aspect 36 wherein the substrate comprises metal, such as aluminum or steel.

[00124] Aspect 38. The method of Aspect 36 wherein the substrate comprises plastic, such as polycarbonate.

[00125] Aspect 39. A substrate coated according to the method of Aspects 36-38.

[00126] Aspect 40. An article comprising the substrate of Aspect 39.

[00127] Aspect 41. The article of Aspect 40, wherein the article comprises a battery, such as a lithium-ion battery. [00128] Aspect 42. The article of Aspect 41 , wherein the battery comprises exterior wall elements defining a housing and optionally interior wall elements, wherein the coating composition or film or sheet is at least partially applied to the external and/or internal side of any of the exterior wall elements and/or to any side of any of the interior wall elements, if present.

[00129] Aspect 43. The article of Aspect 42, wherein any of the exterior wall and/or interior wall elements comprises composite, steel, aluminum, and/or polycarbonate.

[00130] Aspect 44. The article of any of Aspects 40-43, further comprising one or more fire-retardant materials and/or fire mitigation means inside and/or outside the battery.

[00131] Aspect 45. The article of Aspect 44, wherein the fire-retardant materials and/or fire mitigation means comprises a thermally insulating material, a reinforcing material, such as fiberglass, mineral wool, silica/silica fibers, alumina, Kevlar, Nomex, calcium-silicate, or calcium silicate fibers; foam, such as polyurethane/polyurea foam with fire retardants; and/or physical barriers, such as cooling fins, mica boards, Aerogel blankets, and/or mineral/glass/carbon fiber-containing blankets.

[00132] Aspect 46. The article of Aspect 40, wherein the article comprises a vehicle.

[00133] Aspect 47. The article of Aspect 46, wherein the vehicle has a surface coated at least in part with a fire-resistant ecoat.

[00134] Aspect 48. The article of Aspect 47, wherein the fire-resistant ecoat is deposited from an electrodepo sitable composition comprising a fire-retardant pigment.

[00135] Aspect 49. The article of Aspect 48, wherein the fire-resistant ecoat comprises an inorganic, platelike pigment, such as a phyllosilicate pigment.

[00136] Aspect 50. The article of any of Aspects 47-49, wherein the fire-resistant ecoat has a pigment-to-binder (P:B) ratio of 0.4: 1 or higher.

[00137] Aspect 51. The article of Aspect 50, wherein the fire-resistant ecoat has a pigment-to-binder (P:B) ratio of 0.5:1.

[00138] Aspect 52. The article of any of Aspects 49- 51, wherein the fire-resistant ecoat has a pigment-to-binder (P:B) ratio of up to 2.0:1.

[00139] Aspect 53. The article of any of Aspects 46-52, wherein the vehicle has a surface coated at least in part with a flame-retardant adhesive, such as one formulated as a sealant, gap filler, pottant, and/or encapsulant, such as one formed from a composition comprising a flame retardant. [00140] Aspect 54. The article of Aspect 40, wherein the article comprises a structure.

[00141] Aspect 55. The article of Aspect 40, wherein the article comprises an energy storage device other than a battery.

[00142] Aspect 56. A vehicle comprising a surface coated, at least in part, with the composition, sheet or film of any of Aspects 1-35, and an electric battery, wherein the composition, sheet or film is between the surface and the battery.

[00143] Aspect 57. The vehicle of Aspect 56, wherein the vehicle comprises at least one flammable coating, such as a cataphoretic coating, and the composition, sheet or film is between the cataphoretic coating layer and the battery.

[00144] Aspect 58. The vehicle of Aspect 56, further comprising fire-resistant ecoat.

[00145] Aspect 59. The vehicle of Aspect 58, wherein the fire-resistant ecoat is deposited from an electrodepositable composition comprising a fire-retardant pigment.

[00146] Aspect 60. The vehicle of Aspect 59, wherein the fire-resistant ecoat comprises an inorganic, platelike pigment, such as a phyllosilicate pigment.

[00147] Aspect 61. The vehicle of any of Aspects 58-60, wherein the fire-resistant ecoat has a pigment-to-binder (P:B) ratio of 0.4: 1.0 or higher.

[00148] Aspect 62. The vehicle of any of Aspects 58-60, wherein the fire-resistant ecoat has a pigment-to-binder (P:B) ratio of 0.5: 1.0 or higher.

[00149] Aspect 63. The vehicle of any of Aspects 58-60, wherein the fire-resistant ecoat has a pigment-to-binder (P:B) ratio of up to 2.0: 1.0.

[00150] Aspect 64. The article of any of Aspects 46-55 or the vehicle of any of Aspect 56-63, wherein the vehicle has a surface coated at least in pail with a flame-retardant adhesive, such as one formulated as a sealant, gap filler, pottant, and/or encapsulant, such as one formed from a composition comprising a flame retardant.

EXAMPLES

[00151] The following examples are intended to illustrate the disclosure and should not be construed as limiting the disclosure in any way.

Examples

[00152] Coating formulation Examples 1 and 2 were prepared using an epoxy component and amine component standard in the intumescent coatings art as described below. Wt.% is based on the total weight of both the base and hardener. Example 1 contained approximately 50 wt.% ATH and Example 2 contained approximately 40 wt.% ATH. The ATH for each example was spread between the two components as indicated. The Thermal Runaway Test was carried out by applying the coating on top of a first 0.8 mm electro-coated steel panel and curing to a 2 mm DFT. A second 0.8 mm electro-coated steel panel was used to cover the top of the coating with no gap in between. The bottom of panel 1 was heated with 1400-1500°C acetylene fire, and the temperature on the top side of panel 2 was monitored with a thermal couple. During the test, the thermal couple of Example 1 reached a temperature of 238.3°C, while the outer surface of Example 2 reached a temperature of 390°C. The coating according to the present disclosure (Example 1) with greater than 45 wt.% of water-generating material had a temperature reduction of more than 30% as compared with the coating having only 40 wt.% water-generating material.

Example 1 - base (base: hardener = 1:1)

¹ Hexion

² Gabriel performance products

³ Nippon electric glass

⁴ Elementis Specialties

⁵ Wego Chemical Group

Example 1 - hardener (base: hardener = 1:1)

⁶ Huntsman

⁷ Huntsman

⁸ BASF Example 2 - base (base: hardener = 1:1)

Example 2 - hardener (base: hardener = 1:1)

[00153] Whereas particular examples of this disclosure have been described above for purposes of illustration, it will be evident to those skilled in the art that numerous variations of the details of the present disclosure may be made without departing from the disclosure as defined in the appended claims.

Claims

What is claimed is:

1. A coating composition comprising: a) a film forming component; and b) a water-generating material in an amount of 45 wt.% or greater based on total solids of the coating, wherein the coating is non-intumescent.

2. The coating composition of Claim 1, wherein the water generating material is present in an amount of 45 to 70 wt.%, where wt.% is based on total solid weight of the composition.

3. The coating composition of any preceding claim, further comprising a borate source, a silica source, a zinc source, an acid source, a metal oxide that is not a water-generating material, titanium isopropoxide, a carbon source, inorganic fillers, glass fibers and/or mineral fibers, rheology additives, organic solvents, pigments, foam stabilizers, or combinations thereof.

4. The coating composition of Claim 3, comprising one or more of these additives in a total amount of 2-20 wt. %, where wt.% is based on the total solid weight of the composition.

5. The coating composition of any preceding claim in which the film- forming component comprises an epoxy resin and amine crosslinker, and the water-generating material comprises a hydrated metal oxide.

6. The composition of any preceding claim, wherein the composition is substantially free, essentially free, and/or completely free of one or more of the following: a borate source, alkyl phosphorus acid(s), a melamine or melamine derivative, residues of ethylenically unsaturated monomer such as those from (meth)acrylic and/or styrene, a surfactant including, but not limited to, a non-ionic surfactant, silicates including, but not limited to, layered silicate, and aluminum silicate(s), piperazine salt(s), a reinforcing filler, such as fibers, and/or a solvent.

7. A self- supported film or sheet formed from the coating composition of any preceding claim.

8. The coating or self-supported film or sheet of Claims 1-7 where the coating/film/shcct is a protective coating as determined according to the Thermal Runaway Test.

9. A method for using the coating composition or the film or sheet of Claims 1-8 to coat a substrate comprising applying to at least a portion of the substrate, the coating composition, film, or sheet.

10. The method of Claim 9, wherein the substrate comprises metal, such as aluminum or steel, and/or plastic, such as polycarbonate, and/or composite.

11. A substrate coated according to the method of any of Claims 9 or 10.

12. An article comprising the substrate of Claim 11.

13. The article of Claim 12, wherein the article comprises an energy storage device such as a battery, such as a lithium-ion battery.

14. The article of Claim 13, wherein the battery comprises exterior wall elements defining a housing and optionally interior wall elements, wherein the coating composition or film or sheet is at least partially applied to the external and/or internal side of any of the exterior wall elements and/or to any side of any of the interior wall elements, if present.

15. The article of Claims 13-14, further comprising one or more fire-retardant materials and/or fire mitigation means inside and/or outside the battery, such as a thermally insulating material; a reinforcing material, such as fiberglass, mineral wool, silica/silica fibers, alumina, Kevlar, Nomex, calcium- silicate, or calcium silicate fibers; foam, such as poly urethane/poly urea foam with fire retardants; and/or physical barriers, such as cooling fins, mica boards, Aerogel blankets, and/or mineral/glass/carbon fiber-containing blankets.

16. The article of Claim 12, wherein the article comprises a vehicle.

17. The article of Claim 16, wherein the vehicle has a surface coated at least in part with a fire-resistant ecoat and/or a flame-retardant adhesive.

18. The article of Claim 17, wherein the fire-resistant ecoat comprises an inorganic, plate-like pigment and a P:B ratio of 0.4: 1 or higher.

19. The article of Claim 12, wherein the article comprises a structure.

20. A vehicle comprising a surface coated, at least in part, with the composition, sheet or film of any of Claims 1-8, and an electric battery, wherein the composition, sheet or film is between the surface and the battery.

21. The vehicle of Claim 20, wherein the vehicle comprises at least one flammable coating, such as a cataphoretic coating, and the composition, sheet or film is between the cataphoretic coating layer and the battery.

22. The vehicle of Claim 20, wherein the vehicle comprises a fire-resistant ecoat; such as one deposited from an electrodepositable composition comprising a fire-retardant pigment, an inorganic, platelike pigment, such as a phyllosilicate pigment, and/or having a pigment-to-binder (P:B) ratio of 0.4: 1.0 or higher, such as 0.5: 1.0, such as 2.0: 1.0, and/or a flame-retardant adhesive, such as one formulated as a sealant, gap filler, pottant, and/or encapsulant, such as one formed from a composition comprising a flame retardant.