Expansion coating

Abstract

Intumescent coating compositions comprising TiO2 in an amount of 5-20 wt %, a phosphate source in an amount of 20-55 wt %, based on total solids weight, and a borate source, an aluminum source, and / or a silica source are disclosed, along with methods for using such compositions and substrates coated therewith.

Description

Technical Field

[0001] The present invention is directed to an intumescent coating composition, a method for coating a substrate with the composition, a substrate coated with the composition, and an article comprising the substrate including a battery.

Background Art

[0002] Intumescent coatings have been used in various structural applications to protect against both cellulose fires and hydrocarbon fires. Such coatings provide protection by forming charred carbon when exposed to intense heat. The char formed in a fire provides optimal protection when the char expands to an optimal thickness and adheres to the substrate and / or when the char is formed at a thickness such that direct flame impingement does not compromise the integrity of the char, such as by leaving cracks in the char. Many substrates, including structural building components used in commercial and transportation infrastructure such as hotels, airports, concert halls or offshore sites, chemical plants, oil drilling equipment, etc., that would be exposed to extremely high heat in the event of a fire, can benefit from being coated with such coatings. Batteries, such as lithium-ion batteries, can also be exposed to such intense heat, and many batteries, and particularly lithium-ion batteries, are vulnerable to thermal runaway, during which heat and gas are rapidly discharged from the battery, creating a fire hazard. Conventional single-pack fireproof coatings are not excellent in weather resistance, while two-pack fireproof coatings are too viscous to be applied in a thin thickness, and thus, an improved fire-resistant coating, including those used for batteries, is desired.

Summary of the Invention

[0003] The present invention relates to a coating composition comprising a) a film-forming component, b) a phosphate source, c) a borate source, an aluminum source, and / or a silica source, d) TiO2, and e) a gas source, wherein, based on the total solid weight of the composition, TiO2 is present in an amount of 5 to 20% by weight, such as 9 to 15% by weight; the phosphate source is present in an amount of 20 to 55% by weight, such as 25 to 40% by weight or 40 to 55% by weight; if component c contains a borate source, TiO2 is present in an amount of 5 to 20% by weight, such as 9 to 15% by weight; if component c contains an aluminum source, TiO2 is present in an amount of 0.1 to 10% by weight, such as 0.2 to 8% by weight; and if component c contains a silica source, TiO2 is present in an amount of 0.1 to 5% by weight, such as 0.4 to 1% by weight. The composition can be formed into a self-supporting film or sheet. The present invention also includes methods for coating a substrate using a coating composition according to the present invention or a film or sheet formed therefrom as described herein, and substrates coated thereby, as well as articles containing such coated substrates / films or sheets as described in the appended claims, and includes battery components and batteries at least partially coated with the composition, as well as batteries containing the self-supporting film or sheet of the present invention.

[0004] The present invention will be discussed in more detail below. Brief explanation of the drawing

[0005] Table 1 includes photographs of substrates coated with experimental or comparative expansion coating compositions 1-13 after the coated substrates were exposed to a torch flame at 1200±50°C for 10 minutes. Composition 6 also includes a side view of the coated panel after exposure to the torch flame. [Modes for carrying out the invention]

[0006] The present invention relates to a coating composition comprising a) a film-forming component, b) a phosphate source, c) a borate source, an aluminum source, and / or a silica source, d) TiO2, and e) a gas source, wherein, based on the total solid weight of the composition, TiO2 is present in an amount of 5 to 20% by weight, such as 9 to 15% by weight; the phosphate source is present in an amount of 20 to 55% by weight, such as 25 to 40% by weight or 40 to 55% by weight; if component c contains a borate source, it is present in an amount of 5 to 20% by weight, such as 9 to 15% by weight; if component c contains an aluminum source, it is present in an amount of 0.1 to 10% by weight, such as 0.2 to 8% by weight; and if component c contains a silica source, it is present in an amount of 0.1 to 5% by weight, such as 0.4 to 1% by weight. It will be understood that the total solid weight of the composition before curing is the same as the total solid weight after curing.

[0007] Using this coating composition, an expanding coating can be formed. That is, the coating undergoes expansion and carbonization when exposed to heat, such as the high temperatures experienced during a fire. The inventors have discovered that by using a borate source, an aluminum source, and / or a silica source within the range given above in combination with TiO2 and a phosphate source, an expanding coating with desirable carbonization along with desirable adhesion to the substrate is given. "Desirable carbonization" means that the carbon is not easily cracked or removed by direct flame blasting, and the expansion coefficient, which is the ratio between the thickness of the carbon and the thickness of the coating film, can be 5 to 25, such as 7 to 20. "Desirable adhesion" means that the carbon remains substantially intact during direct flame blasting, and there is no apparent detachment of the carbon from the substrate during or after the fire test. Thus, the coating composition according to the present invention offers advantages over conventional expanding coating compositions.

[0008] The coating composition contains a film-forming component. “Film-forming” means that, upon drying and / or curing, the composition can form a continuous film on a surface. The film-forming component may include, for example, a film-forming resin and a crosslinking agent for this purpose. Any film-forming resin can be used according to the present invention. Such a resin can react with itself, i.e., undergo a self-crosslinking reaction, or react with a crosslinking agent to form a film. Such reactions can occur at ambient temperature or high temperatures. “Crosslinking agent” and similar terms, curing agent and hardener, may be used interchangeably herein.

[0009] Examples of suitable resins, 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, can be used as film-forming components. Among these resins, epoxy resins, acrylic resins, and / or polyurethane resins are particularly preferred.

[0010] The film-forming resin used in accordance with the present invention contains one or more functional groups that react with each other or with functional groups on the crosslinking agent. Examples of suitable functional groups include, for example, ketones, hydrazides, carbodiimides, oxazolines, epoxys, amines, vinyls, amides, carbamates, ureas, mercaptans, carboxylic acids, (meth)acryloyls, isocyanates, alkoxysilyls, anhydrides, hydroxyls, and alkoxy groups, functional groups, and combinations thereof.

[0011] Suitable functional groups that can react with each other include, for example, N-methylolamide groups, hydrolyzable or condensable groups bonded to silicon, such as silane groups having chloro, hydroxy, alkoxy, acetoxy, and / or ketoxymo groups, such as ethylenically unsaturated fatty acid groups, azomethine groups, azetidine groups that can be oxidized and dried by air-oxygen, and groups that can undergo a thermoreversible Diels-Alder reaction, such as furan / maleimide. If the resin contains functional groups that can react with each other, it is considered self-crosslinkable, and the presence of a curing agent is not required to provide the expansion composition.

[0012] This resin may also contain a combination of functional groups that can react with each other (self-crosslink) and functional groups that are reactive with the functional groups of the curing agent. In such cases, if a curing agent is present, two crosslinking mechanisms will occur during curing: a reaction between the functional groups on the crosslinking agent and the resin, and a self-crosslinking reaction of the resin itself.

[0013] A suitable epoxy resin for use in the present invention comprises at least one polyepoxide. The polyepoxide typically has at least two 1,2-epoxy groups. The epoxy equivalent of the polyepoxide may range from 80 to 6000, such as 100 to 700. The epoxy compound may be saturated or unsaturated cyclic, aliphatic, alicyclic, aromatic, or heterocyclic. These may contain substituents such as halogens, hydroxyls, and ether groups.

[0014] Suitable examples of polyepoxides are those having more than 1, or usually 2, 1,2-epoxy equivalents, i.e., polyepoxides having an average of 2 epoxy groups per molecule. The most commonly used polyepoxides are polyglycidyl ethers of polyphenols such as 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), resorcinol, hydroquinone, benzenedimethanol, phloroglucinol, bisphenol F, and catechol, or polyglycidyl ethers of polyols such as alicyclic polyols such as 1,2-cyclohexanediol, 1,4-cyclohexanediol, 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 1,2-bis(hydroxymethyl)cyclohexane. Examples of aliphatic polyols include, in particular, trihydroxymethylpentanediol, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-butylene glycol, 1,5-pentanediol, 1,2,6-hexanetriol, cyclohexanedimethanol, glycerol, trimethylolpropane, hydrogenated bisphenol A, hydrogenated bisphenol F, or polyether glycols, such as poly(oxytetramethylene) glycol, poly(oxyethylene) glycol, poly(oxypropylene) glycol, and neopentanediol.

[0015] Another group of suitable epoxy resins includes polyglycidyl ethers of polycarboxylic acids formed by the reaction of epoxy compounds such as epichlorohydrin with aliphatic or aromatic polycarboxylic acids such as oxalic acid, succinic acid, glutaric acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, or dimerized linoleic acid. Such resins are commercially available from Hexion Inc. under their EPIKOTE and EPON lines.

[0016] Other suitable epoxy resins that can be used in accordance with the present invention include epoxidized olefinic unsaturated alicyclic materials such as epoxy alicyclic ethers and esters, epoxy resins containing oxyalkylene groups, and epoxy novolac resins, which are prepared by reacting epihalohydrins with condensation products of aldehydes and monovalent or polyvalent phenols, and include epoxyphenol novolac resins or epoxy cresol novolac resins.

[0017] Furthermore, according to the present invention, it may be advantageous to use a flexible polyepoxy resin as the polyepoxy-functional compound in the expanding composition of the present invention. These resins are generally essentially linear materials, although a small amount of branching is permissible. Examples of suitable materials include dimer acid-based materials such as epoxidized soybean oil and EMPOL1010 resin, which is commercially available from BASF SE (Ludwigshafen, Germany), as well as rubber-modified polyepoxy resins such as products prepared from polyglycidyl ethers of bisphenol A and acid-functionalized polybutadienes.

[0018] Other suitable examples of flexible polyepoxides for use in accordance with the present invention include flexible acid-functional polyesters and epoxy-functional adducts prepared from polyepoxides. Acid-functional polyesters may have an acid value of at least 10 mg KOH / g, such as 140–350 mg KOH / g or 180–260 mg KOH / g, as determined by ASTM 974-87.

[0019] For use in this specification, linear polyesters may be preferred over branched polyesters. Acid-functional polyesters can be prepared by polyesterizing organic polycarboxylic acids or their anhydrides with organic polyols. The polycarboxylic acids and polyols may be aliphatic or aromatic dibasic acids and diols.

[0020] Diols that can be used in the production of polyesters include alkylene glycols such as ethylene glycol, diethylene glycol, and neopentyl glycol, and other diols such as hydrogenated bisphenol A, cyclohexanediol, cyclohexanedimethanol, and caprolactonediol, for example, reaction products of epsilon-caprolactone and ethylene glycol, hydroxyalkylated bisphenols, and polyether glycols, such as poly(oxytetramethylene) glycol, poly(oxyethylene) glycol, and poly(oxypropylene) glycol. Diols are more preferred, but polyols with higher functionalities can also be used. Examples include trimethylolpropane, trimethylolethane, pentaerythritol, glycerol, isosorbide, tetramethylcyclobutanediol, and polyols with higher molecular weights, such as those produced by oxyalkylating lower molecular weight polyols.

[0021] The acid component of the polyester may include dicarboxylic acids or anhydrides of monomers 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, decandioic acid, dodecandioic acid, rosinic acid, diphenolic acid, gallic acid, and various other types of dicarboxylic acids, such as unsaturated C 18 Examples include Diels-Alder adducts of fatty acids.

[0022] Polyesters may contain small amounts of monobasic acids such as benzoic acid, stearic acid, acetic acid, hydroxystearic acid, and oleic acid. Higher polycarboxylic acids, such as trimellitic acid, may also be used. Where acids are referred to above, it is understood that the anhydrides of these acids, which form anhydrides, can be used in place of the acids. Lower alkyl esters of acids, such as dimethyl glutarate and dimethyl terephthalate, can also be used.

[0023] According to the present invention, the polyester used to prepare the epoxy-functional adduct can be prepared from a polycarboxylic acid component containing a polycarboxylic acid or a mixture of acids having 7 to 16 carbon atoms and a polyol component containing a part of diethylene glycol.

[0024] The polyepoxide used to prepare the epoxy-functional adduct of the flexible acid-functional polyester and the polyepoxide can be selected from those defined above for the polyepoxide-functional component according to the present invention.

[0025] Another suitable polyepoxy-functional compound is an epoxy-functional acrylic resin. Such a resin can be prepared by free radical addition polymerization of (meth)acrylic monomers, optionally in combination with vinyl monomers or other monomers containing at least one carbon-carbon double bond, and the monomer composition contains at least one epoxy-functional compound having at least one carbon-carbon double bond.

[0026] Suitable epoxy-functional ethylenically unsaturated monomers include, for example, glycidyl (meth)acrylate, allyl glycidyl ether, vinyl glycidyl ether, vinyl cyclohexene oxide, limonene oxide, 2-ethyl glycidyl acrylate, 2-ethyl glycidyl methacrylate, 2-(n-propyl) glycidyl acrylate, 2-(n-propyl) glycidyl methacrylate, 2-(n-butyl) glycidyl acrylate, 2-(n-butyl) glycidyl methacrylate, glycidyl methyl methacrylate, glycidyl acrylate, (3’,4’-epoxyheptyl)-2-ethyl acrylate, (3’,4’-epoxyheptyl)-2-ethyl methacrylate, (6’,7’-epoxyheptyl) acrylate, (6’,7’-epoxyheptyl) methacrylate, allyl-3,4-epoxyheptyl ether, 6,7-epoxyheptyl allyl ether, vinyl-3,4-epoxyheptyl ether, 3,4-epoxyheptyl vinyl ether, 6,7-epoxyheptyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3-vinyl cyclohexene oxide, alpha-methyl glycidyl methacrylate, 3,4-epoxycyclohexyl methyl (meth)acrylate, and combinations thereof.

[0027] Additional monomers suitable for the preparation of epoxy-functional acrylic resins include, for example, ethylenically unsaturated nitrile compounds, vinyl aromatic monomers, alkyl esters of ethylenically unsaturated acids, hydroxyalkyl esters of ethylenically unsaturated acids, amides of ethylenically unsaturated acids, ethylenically unsaturated acids, ethylenically unsaturated sulfonic acid monomers and / or ethylenically unsaturated phosphorus-containing acid monomers, vinyl carboxylates, conjugated dienes, monomers having at least two ethylenically unsaturated groups, and combinations thereof.

[0028] Examples of ethylenically unsaturated nitrile monomers that can be used in the preparation of epoxy-functionalized acrylic resins include polymerizable unsaturated aliphatic nitrile monomers containing 2 to 4 carbon atoms in a linear or branched arrangement, which may be substituted with either an acetyl group or an additional nitrile group. Such nitrile monomers include acrylonitrile, methacrylonitrile, alpha-cyanoethylacrylonitrile, fumaronitrile, and combinations thereof, with acrylonitrile being particularly preferred.

[0029] Typical suitable vinyl aromatic monomers include, for example, styrene, α-methylstyrene, p-methylstyrene, t-butylstyrene, and vinyltoluene.

[0030] Examples of (meth)acrylic acid esters that can be used in the preparation of epoxy-functionalized acrylic resins include n-alkyl esters, iso-alkyl esters, or tert-alkyl esters of acrylic or (meth)acrylic acid having 1 to 20 carbon atoms in the alkyl group, or reaction products of methacrylic acid with glycidyl esters of neoacids such as versatic acid, neodecanoic acid, or pivalic acid, as well as monomers of hydroxyalkyl (meth)acrylate and alkoxyalkyl (meth)acrylate.

[0031] Suitable alkyl esters of (meth)acrylic acid include, for example, C1-C 10 - C1-C such as alkyl (meth)acrylates. 20Alkyl (meth)acrylates are examples. 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 acid such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and combinations thereof are particularly preferred.

[0032] Examples of hydroxyalkyl (meth)acrylate monomers that can be used in the preparation of epoxy-functionalized acrylic resins include hydroxyalkyl acrylate and methacrylate monomers based on ethylene oxide, propylene oxide, and higher alkylene oxides, or mixtures thereof. Examples include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl acrylate. Particularly preferred is 2-hydroxyethyl (meth)acrylate.

[0033] Examples of ethylenically unsaturated acid amides that can be used in the preparation of epoxy-functionalized acrylic resins include acrylamide, methacrylamide, and diacetone acrylamide.

[0034] Vinyl ester monomers that can be used to prepare epoxy-functionalized acrylic resins include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, vinyl 2-ethylhexanoate, vinyl stearate, and vinyl esters of versatic acid.

[0035] Suitable ethylenically unsaturated carboxylic acid monomers for the preparation of epoxy-functionalized acrylic resins include, for example, monocarboxylic acid and dicarboxylic acid monomers, as well as monoesters of dicarboxylic acids. Particularly preferred are ethylenically unsaturated aliphatic monocarboxylic acids or dicarboxylic acids or anhydrides containing 3 to 5 carbon atoms. Examples of monocarboxylic acid monomers include acrylic acid, methacrylic acid, and crotonic acid, while examples of dicarboxylic acid monomers include fumaric acid, itaconic acid, maleic acid, and maleic anhydride. Other suitable examples of ethylenically unsaturated acids include vinylacetic acid, vinyl lactic acid, vinyl sulfonic acid, 2-methyl-2-propene-1-sulfonic acid, styrene sulfonic acid, acrylamide methylpropane sulfonic acid, and their salts. Suitable ethylenically unsaturated carboxylic acid monomers include (meth)acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, and combinations thereof.

[0036] Suitable conjugated diene monomers for the preparation of epoxy-functionalized acrylic resins include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, 1,3-octadiene, 2-methyl-1,3-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-1,3,6-octatriene, and 2-methyl-6-methylene-1,7- Examples of conjugated diene monomers include octadiene, 7-methyl-3-methylene-1,6-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-1,3,6-octatriene, 3,7,11-trimethyl-1,3,6,10-dodecatetraene, 7,11-dimethyl-3-methylene-1,6,10-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, as well as combinations thereof.

[0037] It is also possible to use combinations of two or more different polyepoxy functional compounds in the film-forming components, such as three or more, or four or more, including any of those disclosed above.

[0038] Suitable polyepoxy-functional compounds used in accordance with the present invention include, for example, diglycidyl ethers of bisphenol A, diglycidyl ethers of bisphenol F, resorcinol diglycidyl ethers, epoxyphenol novolac resins, epoxy cresol novolac resins, epoxy-functional (poly)siloxanes, epoxy-functional polysulfides, epoxy-functional adducts of acid-functional polyesters, and polyepoxides, as mentioned above. Examples of acrylic resins used in the present invention include copolymers of one or more alkyl esters of acrylic acid or methacrylic acid together with one or more other polymerizable ethylenically unsaturated monomers as needed. Useful alkyl esters of acrylic acid or methacrylic acid include, for example, aliphatic alkyl esters containing 1 to 30 and 4 to 18 carbon atoms in the alkyl group. Non-limiting examples include, for example, methyl methacrylate, ethyl methacrylate, butyl methacrylate, ethyl acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Other suitable copolymerizable ethylenically unsaturated monomers include, for example, vinyl aromatic compounds such as styrene and vinyltoluene, 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.

[0039] Acrylic copolymers can contain 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 hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, caprolactone and hydroxyalkyl acrylate hydroxy functional adducts, as well as the corresponding methacrylates, and hydroxyalkyl acrylates and methacrylates that typically have 2 to 4 carbon atoms in the hydroxyalkyl group, such as the beta-hydroxyester functional monomers described below. Acrylic polymers can also be prepared with N-(alkoxymethyl)acrylamide and N-(alkoxymethyl)methacrylamide.

[0040] Beta-hydroxyester functional monomers can be prepared from ethylenically unsaturated epoxy functional monomers and carboxylic acids having 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 ethylenically unsaturated acid functional monomers.

[0041] The polymer of the film-forming resin used in the present invention may also be polyurethane. Among the polyurethanes that can be used are polymer polyols prepared by reacting polyester polyols or acrylic polyols, such as those mentioned above, with polyisocyanates, such that the OH / NCO equivalent ratio exceeds 1:1, and as a result free hydroxyl groups are present in the product.

[0042] According to the present invention, the film-forming component may include, for example, a combination of an epoxy resin and an acrylic resin, or an epoxy resin and a polyurethane resin, as disclosed in US5,108,832 or US5,070,119.

[0043] If the film-forming component includes an epoxy resin and a polyamine and / or polythiol-functional compound as a curing agent, as discussed below, the film-forming component may further include (i) a beta-hydroxy ester of (meth)acrylic acid, (ii) a (meth)acrylate-functional compound different from compound (i), or a combination thereof.

[0044] The beta-hydroxyesters of (meth)acrylic acid may include multiple beta-hydroxyesters of (meth)acrylic ester groups resulting from the reaction of polyepoxides with (meth)acrylic acid. Polyepoxides can be reacted with (meth)acrylic acid in an epoxy-carboxylic acid equivalent ratio of 1:0.1 to 1:1.2, preferably 1:0.5 to 1:1.2, and more preferably 1:1 to 1:1.05. Particularly preferred beta-hydroxyesters of (meth)acrylic acid are the reaction products of EPIKOTE828 (a reaction product of bisphenol A and epichlorohydrin) and acrylic acid (commercially available from Allnex as EBECRYL3720).

[0045] The polyepoxides that can be used as reaction products with (meth)acrylic acid are the polyepoxides disclosed above.

[0046] In addition to (meth)acrylic acid beta-hydroxyester (i), or alternatively, a different (meth)acrylate functional compound (ii) may be present in the film-forming component. This allows the viscosity of the expanding composition of the present invention to be adjusted. Therefore, component (ii), as needed, is considered to function as a reactive diluent in the expanding composition of the present invention. Examples of (meth)acrylate functional components (ii) as needed for the expanding composition of the present invention include 1,4-butanediol, neopentyl glycol, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, paraxylene glycol, 1,4-cyclohexanediol, trimethylolethane, trimethylolpropane, pentaerythritol, polyether glycol, for example, poly(oxytetramethylene) glycol, poly(oxyethylene) glycol, poly(oxypropylene) glycol, and poly(meth)acrylates of combinations thereof.

[0047] As described above, the film-forming component may also include a crosslinking agent. Any suitable crosslinking agent can be used in accordance with the present invention and will be selected by those skilled in the art to react with the functional groups of the film-forming resin. Suitable curing agents include, for example, polyamines, such as polyetheramines, polyamides, polyepoxides, aminoplast resins, phenolic resins, polyisocyanates, polythiols, and polyols.

[0048] The curing agent may be a latent or blocking curing agent, in which the actual functional groups that are reactive with the functional groups of the film-forming resin are generated or restored by a deblocking reaction under curing conditions such as high temperature. A suitable curing agent of this type is, for example, a blocked polyisocyanate. Thus, as used herein, the term polyisocyanate encompasses both blocked and free polyisocyanates. Latent or blocking curing agents are particularly suitable for providing single-component compositions to ensure sufficient storage stability and pot life before application and curing.

[0049] Examples of polyamine curing agents include aliphatic polyamines, aromatic polyamines, polyamine amides, polyetheramines (e.g., those commercially available from Huntsman Cooperation (The Woodlands, Texas)), polysiloxaneamines, polysulfideamines, or combinations thereof. Examples include diethyltriamine, 3,3-amino-bis-propylamine, triethylenetetraamine, tetraethylenepentamine, m-xylenediamine, isophoronediamine, 1,3-bis(aminoethyl)cyclohexane, bis(4-aminocyclohexyl)methane, N-aminoethylpiperazine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-3,3'-diethyldiphenylmethane, and diaminodiphenylsulfone, and reaction products of polyamines with aliphatic fatty acids, such as a series of materials sold by BASF under the trademark VERSAMID, the latter of which are particularly preferred.

[0050] In addition, any of the above-mentioned polyamine adducts can be used. These polyamine adducts are formed by reacting a polyamine with a suitable reactive compound, such as an epoxy resin. This reaction reduces the free amine content in the curing agent, making it more useful in low-temperature and / or high-humidity environments.

[0051] As a curing agent, various polyetheramines such as Jeffamine D-230, Jeffamine D-400, Jeffamine 600, Jeffamine 1000, Jeffamine 2005, and Jeffamine 2070, etc., available from Huntsman Corp., may be used.

[0052] Various polyamides can also be used as curing agents. Generally, polyamides contain reaction products of dimer fatty acids, polyethyleneamines, and small amounts of monomeric fatty acids. Dimer fatty acids are prepared by oligomerization of monomeric fatty acids. Polyethyleneamines may be any higher polyethyleneamines such as diethylenetriamine, triethylenetetraamine, or tetraethylenepentaamine, with diethylenetriamine being the most commonly used. Using polyamides as curing agents can impart one or more desirable properties to the coating, such as corrosion resistance, water resistance, and / or good flexibility.

[0053] Useful polythiol compounds as curing agents 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).

[0054] As mentioned above, when the film-forming resin includes an epoxy resin, polyamines, polythiol compounds, or combinations thereof can be used as crosslinking agents.

[0055] In the coating composition of the present invention, when an epoxy resin is used, the equivalent ratio of the combined functional groups in the film-forming resin, such as epoxy groups, to the functional groups in the curing agent may be 2:1 to 1:2, such as 1.05:1.0 to 1:2 or 1:1.4 to 1:2.

[0056] The coating composition may contain film-forming components in any appropriate amount. For example, the coating composition may contain 20% by weight or more than 20% by weight of film-forming components, such as 30% by weight or more than 30% by weight, or 40% by weight or more than 40% by weight. The coating composition may contain 60% by weight or less than 60% by weight of film-forming components, such as 50% by weight or less than 50% by weight, or 40% by weight or less than 40% by weight. The coating composition may contain film-forming components in amounts within a range of any of the values ​​mentioned above, such as 20% by weight to 60% by weight, 20% by weight to 40% by weight, or 30% by weight to 50% by weight. Unless otherwise indicated, the weight percentages reported herein are based on the total solid weight of the composition.

[0057] The coating composition of the present invention further comprises a phosphate source. As used herein, the phosphate source means any phosphorus-containing material, including phosphoric acid, its condensation or dehydration products (including oxides), or any salt, ester, amide, or other derivative thereof. The phosphate source may include, for example, phosphoric acid, monoammonium phosphate and diammonium phosphate, triphenyl phosphate, tris-(2-chloroethyl) phosphate, tri(2-chloroisopropyl) phosphate, phosphorus-containing amides such as phosphorylamide, and various materials such as melamine pyrophosphate. Preferably, the phosphorus source is of formula (NH4) n+2 P n O 3n+1The present invention provides an ammonium polyphosphate represented by the formula, where n is at least an integer of 2, preferably at least an integer of 50. The expansion composition of the present invention may contain a phosphate source in an amount of 20% by weight or more than 20% by weight, such as 25% by weight or more than 25% by weight, or 30% by weight or more than 30% by weight, 35% by weight or more than 35% by weight, or 40% by weight or more than 40% by weight. The coating composition may contain a phosphate source in an amount of 55% by weight or less than 55% by weight, such as 50% by weight or less than 50% by weight, or 45% by weight or less than 45% by weight, or 40% by weight or less than 40% by weight, or 35% by weight or less than 35% by weight. The coating composition may contain a phosphate source in an amount in the range of 20 to 55% by weight, for example, 25 to 40% by weight, or 40 to 55% by weight, among any of the values ​​mentioned above. Each weight percent reported herein is based on the total solid weight of the composition. Phosphorus is thought to function as a carbon accelerator in expanding compositions.

[0058] The coating composition of the present invention further comprises at least one of a borate source, an aluminum source, and / or a silica source. Therefore, the coating composition of the present invention may contain, for example, one of a borate source, an aluminum source, or a silica source. For example, the coating composition may contain a borate source as component c. Alternatively, the coating composition may contain an aluminum source or a silica source as component c. On the other hand, the coating composition may also contain two or more combinations of a borate source, an aluminum source, and / or a silica source. For example, the coating composition according to the present invention may contain an aluminum source and a silica source. As used herein, a borate source means any boron-containing material containing boric acid, or its condensation or dehydration products (including oxides), or a salt or ester of any of the foregoing. Suitable borate sources include, for example, metallic borates such as ammonium pentaborate, boric acid, and zinc borate; borates such as boron oxide, sodium borate, potassium borate, and ammonium borate; borate esters such as butyl borate or phenyl borate; and combinations thereof. As used herein, an aluminum source means any aluminum-containing material. Typically, an aluminum source may be an aluminum compound, particularly an inorganic aluminum compound. Suitable aluminum sources include, for example, aluminum hydroxide, aluminum oxide (alumina), aluminum chloride, aluminum salts, and combinations thereof. As an example, an aluminum source may include aluminum hydroxide and / or aluminum oxide. As used herein, a silica source means any silicon-containing material containing polysiloxane, silane, silicic acid, their condensation or dehydration products (including oxides), or salts or esters of any of the aforementioned. Suitable silica sources include, for example, fumed silica or quartz with particle sizes less than 150 μm, or silica-containing materials such as benton or kaolin.

[0059] The expansion composition of the present invention, when used, may contain a borate source in an amount exceeding 5% by weight or 5% by weight, for example, 6% by weight or 6% by weight, for example, 7% by weight or 7% by weight, for example, 8% by weight or 8% by weight, for example, 9% by weight or 9% by weight, for example, 10% by weight or 10% by weight. The coating composition may contain a borate source in an amount less than 20% by weight, such as 19% by weight or less than 19% by weight, or 18% by weight or less than 18% by weight, or 15% by weight or less than 15% by weight. The coating composition may contain a borate source in an amount in the range of any of the values ​​mentioned above, such as 5% to 20% by weight, or 6% to 15% by weight, or 9% to 15% by weight. The expansion composition of the present invention, when used, may contain an aluminum source in an amount exceeding 0.1% by weight or 0.1% by weight, such as 0.2% by weight or more, 0.3% by weight or more, 0.5% by weight or more, 1% by weight or more, 3% by weight or more, or 5% by weight or more. The coating composition may contain an aluminum source in an amount less than 10% by weight or 10% by weight, such as 9% by weight or less, 8% by weight or less, 5% by weight or less, 3% by weight or less, 1% by weight or less, or 0.7% by weight or less. The composition may contain an aluminum source in an amount in the range of any of the values ​​mentioned above, such as 0.1% to 10% by weight, such as 0.2% to 8% by weight, or 0.3% to 1% by weight. When used, the expansion composition of the present invention may contain a silica source in an amount exceeding 0.1% by weight or 0.1% by weight, such as 0.2% by weight or more, 0.3% by weight or more, 0.4% by weight or more, or 0.5% by weight or more.The coating composition may contain a silica source in an amount of 5% by weight or less than 5% by weight, such as 3% by weight or less than 3% by weight, 2% by weight or less than 2% by weight, 1% by weight or less than 1% by weight, or 0.8% by weight or less than 0.8% by weight. The composition may contain a silica source in an amount in the range of any of the values ​​mentioned above, such as 0.1 to 5% by weight, or such as 0.4 to 1% by weight. The weight percentages reported above are based on the total solid weight of the composition, respectively.

[0060] The composition of the present invention further comprises titanium dioxide (TiO2). The composition according to the present invention may contain TiO2 in an amount greater than 5% by weight, such as 6% by weight or more than 6% by weight, or 7% by weight or more than 7% by weight, or 8% by weight or more than 8% by weight, or 9% by weight or more than 9% by weight, or 10% by weight or more than 10% by weight. The coating composition may contain TiO2 in an amount less than 20% by weight, such as 19% by weight or less than 19% by weight, or 18% by weight or less than 18% by weight, or 17% by weight or less than 17% by weight, or 15% by weight or less than 15% by weight, or 13% by weight or less than 13% by weight, or 10% by weight or less than 10% by weight. The composition may contain TiO2 in an amount ranging from 5% to 20% by weight, such as 5% to 10% by weight, or 10% to 18% by weight. The weight percentages reported above are based on the total solid weight of the composition.

[0061] As described above, the inventors have found that by using a borate source, an aluminum source, and / or a silica source within the range given above in combination with TiO2 and a phosphate source, an expanded coating having desirable carbon formation along with desirable adhesion to the substrate is obtained. Therefore, the composition offers advantages over similar compositions that lack one or more of the described elements and / or are used outside the range described.

[0062] The coating composition further comprises a gas source. The “gas source” refers to a compound that provides an expanding gas during thermal decomposition. The expanding gas, when exposed to high temperatures or flames, plays a role in foaming and inflating the expanding composition. The resulting carbon is a thick, multi-cell material that provides insulation and protection to the underlying substrate. Any suitable expanding gas source, such as nitrogen-containing materials, can be used in the expanding composition of the present invention. Examples of suitable nitrogen-containing materials include melamine, phosphate salts, guanidine, methylolated melamine, hexamethoxymethylmelamine, urea, dimethylurea, melamine pyrophosphate, dicyandiamide, guanylurea phosphate, and glycine. Other conventional expanding gas sources, such as materials that release carbon dioxide, can also be used. Examples include alkaline earth metals such as calcium carbonate or magnesium carbonate. To create expandable graphite, Compounds that release water vapor when they decompose upon heating, such as calcium hydroxide, magnesium dihydrate, or aluminum trihydrate. messenger It can also be used. Other examples of such compounds are borate sources such as boric acid, as well as borate derivatives such as borate esters and metal borates. Gas sources such as melamine may be used in the expansion composition of the present invention in amounts greater than 1% by weight, such as 2% by weight or more than 2% by weight, or 3% by weight or more than 3% by weight. Compositions according to the present invention may contain a gas source in amounts such as 10% by weight or less than 10% by weight, or 8% by weight or less than 8% by weight, or 7% by weight or less than 7% by weight, or 5% by weight or less than 5% by weight. Compositions may contain a gas source in amounts ranging from 3% to 7% by weight, or 1% to 10% by weight, or any of the values ​​mentioned above. Each reported weight percent is based on the total solid weight of the composition.

[0063] The coatings of the present invention may contain one or more additional additives suitable for use in expansion coatings. Examples of such additives include zinc sources, acid sources, metal oxides, e.g., pre-hydrolyzed tetraethyl orthosilicate, titanium isopropoxide, carbon sources, inorganic fillers, glass fibers and / or mineral fibers, e.g., CHOPVANTAGE from PPG, Coatforce or Roxul fibers from Lapinus, rheological additives, organic solvents, pigments, foam stabilizers, and combinations thereof.

[0064] The zinc source, as needed, can include a variety of materials. The zinc material is thought to contribute to the formation of small cellular structures within the carbon. These small cells in the carbon provide better insulation for the substrate, better maintain the integrity of the carbon, and allow it to adhere to the substrate. Therefore, cracking and fracture of the carbon from the substrate are minimized, providing stronger protection for the underlying substrate. Examples of suitable materials as a zinc source include zinc salts such as zinc oxide, zinc borate, zinc phosphate, and zinc carbonate; zinc metal can also be used.

[0065] The acid source can be selected from ammonium phosphate, ammonium polyphosphate, diamonium diphosphate, diamonium pentaborate, phosphate-producing materials, boric acid, metal or organic borates, and combinations thereof.

[0066] It should be understood that many of the components of this composition may perform more than one function within the composition. For example, phosphorus, zinc, boron, and expanding gas may each be supplied by a different source material, or alternatively, a single material may be a source of more than one of these components. For example, melamine pyrophosphate can provide a source of both phosphorus and expanding gas, zinc borate can provide a source of zinc and borate, zinc phosphate can provide a source of zinc and phosphate, and so on.

[0067] Reinforcing fillers, as needed, can be selected from a number of conventionally used materials, including fibrous and platelet reinforcing agents, which may be preferable to other fillers. Examples of fibrous reinforcing agents include glass fibers, ceramic fibers, e.g., aluminum oxide / silicon oxide, graphite fibers, mineral fibers, and basalt fibers. Examples of platelet reinforcing agents include hammer-milled glass flakes, mica, and wollastonite. Other suitable fillers include metal oxides, clay, talc, silica, diatomaceous earth, LAPINUS fibers, and various pigments. Reinforcing fillers are thought to help control the expansion of the fire-resistant composition before and during char formation, so that the resulting char is hard and uniform. When present, reinforcing fillers such as glass fibers and / or mineral fibers are typically present in the composition in amounts of 5.0% or less by weight, e.g., 4% or less by weight, e.g., 3% or less by weight, based on the total solid weight of the expanded composition. The compositions according to the present invention may contain reinforcing fillers in amounts exceeding 0.1% by weight or 0.1% by weight, such as 0.2% by weight or more, 0.5% by weight or more, or 1% by weight or more. The compositions may contain reinforcing fillers in amounts within a range of any of the values ​​mentioned above, such as 0.1% by weight to 5.0% by weight or 1% by weight to 4% by weight. Each reported weight percent is based on the total solid weight of the composition.

[0068] The expanding compositions of the present invention may also contain various conventional additives such as rheological additives, organic solvents, foam stabilizers, pigments, and flame diffusion control agents. These ingredients are optional and can be added in various amounts. Typically, when additional additives are used, they are present in a total amount greater than 1% by weight, such as 2% by weight or more than 2% by weight, 5% by weight or more than 5% by weight, or 10% by weight or more than 10% by weight. If additional additives are used, they may be present in the composition according to the present invention in an amount less than 20% by weight, such as 15% by weight or less than 15% by weight, or 12% by weight or less than 12% by weight. The composition may contain additional additives as needed in amounts ranging from 1% by weight to 20% by weight, such as 2-20% by weight or 5-15% by weight, or any of the values ​​mentioned above. Each reported weight percent is based on the total solid weight of the composition.

[0069] The expanding composition may be either a single-component composition ("1K") or a multi-component composition, such as a single-component composition ("2K") or a multi-component composition ("2K"). A 1K composition will be understood as a composition in which all coating components are kept in the same container after production, during storage, etc. A 1K composition can be applied to a substrate and cured by any conventional means, such as heating or forced air. The composition may also be multi-component, which will be understood as a composition in which various components are kept separately until immediately before application. The composition may be thermoplastic or thermosetting. For example, the composition may be packaged as a 2K system with a film-forming resin in a first package (A) and a curing agent in a second package (B) for this purpose, thereby all other components used in the coating composition may be used in either package (A) or package (B), or in any combination thereof, or some or all may be in one or more further packages (C). The individual packages are mixed before use of the expanding composition.

[0070] The curable expansion composition of the present invention may be in the form of a thick material such as mastic. The composition is solvent-free and is particularly preferred to be spray-applied. Dilution, if desired, can be achieved with various conventional solvents such as xylene, methylene chloride, or 1,1,1-trichloroethane.

[0071] The curable expansion coating composition of the present invention can be applied to provide various dry film thicknesses as desired. Suitable dry film thicknesses may range from 10 to 20,000 microns, for example, 50 to 5,000 microns, or for example, 100 to 2,000 microns. The desired dry film thickness ("DFT") can be changed depending on the application. When used in building structural components, a DFT in the range of 200 to 20,000 microns, such as 300 to 1,000 microns or 3,000 to 15,000 microns, may be suitable. When used in lithium batteries, a DFT in the range of 200 to 5,000 microns, such as 200 to 1,000 or 1,000 to 5,000, may be suitable.

[0072] Alternatively, the curable expansion composition of the present invention can be formed into a self-supporting film or sheet. The self-supporting film or sheet can then be cured to form a crosslinked expandable self-supporting film or sheet. Generally, the curable expansion composition of the present invention can be formed into a film or sheet by any technique well known to those skilled in the art, such as by a cast molding process or by impregnating a mesh into a coating. The film or sheet can be cured to form a crosslinked expandable self-supporting film or sheet before applying the crosslinked expandable self-supporting film or sheet to a substrate. After the forming step, it is also within the scope of the present invention to apply the uncured film or sheet to a substrate and then cure it to obtain a crosslinked expandable layer according to the present invention. The film or sheet can be applied to a substrate through an adhesive.

[0073] The composition and self-supporting films or sheets can be applied to any substrate known in the art, including electronic devices including consumer electronics, glass and transparent films, and sporting goods including golf balls, such as housings and circuit boards, such as automotive substrates, marine substrates, industrial substrates, heavy machinery, packaging substrates, timber, wooden flooring and furniture, apparel, computers, notebooks, smartphones, tablets, televisions, game consoles, computer equipment, computer accessories, and housings for MP3 players, etc. These substrates may be metallic or non-metallic, for example. Examples of metallic substrates include tin, steel, tin-plated steel, chromium passivated steel, galvanized steel, aluminum, and aluminum foil. As used herein, metal sheets refer to flat metal sheets and coiled metal sheets that are coiled, uncoiled for coating, and then coiled again for shipment to manufacturers. Non-metallic substrates include polymer compounds, plastics, polyesters, polyolefins, polyamides, cellulose compounds, polystyrene, polyacrylics, poly(ethylene naphthalate), polypropylene, polyethylene, nylon, EVOH, polylactic acid, other “environmentally friendly” polymer substrates, poly(ethylene terephthalate) ("PET"), polycarbonate, polycarbonate acrylobutadiene styrene ("PC / ABS"), SMC, carbon fiber, polyamides, wood, veneer, wood composites, particleboard, medium-density fiberboard, cement, stone, glass, paper, corrugated cardboard, textiles, and both synthetic and natural leather. The substrate may be part of a structure or part of a vehicle. As used herein, “structure” means buildings, bridges, transport infrastructure, oil drilling rigs, oil platforms, water towers, power transmission towers, support structures, wind turbines, walls, piers, docks, dikes, dams, shipping containers, trailers, and any part of any metal structure exposed to corrosive environments.As used herein, "vehicle" in its broadest sense refers to all types of vehicles, including but not limited to cars, trucks, buses, tractors, harvesters, heavy machinery, vans, golf carts, motorcycles, bicycles, railway cars, subway cars, airplanes, helicopters, and boats of all sizes.

[0074] The substrate may be a substrate that has already been treated in some way to impart a visual and / or color effect. For example, the substrate may be treated before application of the coating composition by alkaline cleaning, deoxygenation, mechanical cleaning, ultrasonic cleaning, solvent wiping, roughing, plasma cleaning or etching, exposure to chemical vapor deposition, treatment with adhesion promoters, plating, anodizing, annealing, cladding, or any combination thereof. The substrate may be treated using any of the above methods before application of the coating composition, such as by immersing the substrate in a cleaning bath and / or deoxidizing bath before application of the coating composition. The substrate may also be plated before application of the coating composition. As used herein, “plating” refers to depositing a metal by covering the surface of the substrate. The substrate may also be 3D printed.

[0075] As discussed above, the base material may include a battery or battery components. A battery may be, for example, a battery for an electric vehicle, and a battery component may be a battery component for an electric vehicle. A "battery component" may be any component found within a battery, such as a lithium-ion battery. Battery components may include, for example, electrodes, battery cells, battery shells, battery modules, battery packs, battery boxes, battery cell casings, pack shells, battery covers and trays, thermal management systems, battery housings, module housings, module racking, battery side plates, battery cell housings, cooling modules, cooling tubes, cooling fins, cooling plates, busbars, battery frames, electrical connections, metal wires, or copper or aluminum conductors or cables.

[0076] Accordingly, the present invention further covers articles coated at least partially with the coating composition of the present invention. The coating composition of the present invention can be applied to an article in any form, such as a coating composition or a crosslinked expandable self-supporting film or sheet. When referring to a film or sheet, "applied" and any variation thereof means that the film / sheet can be attached to the article by an adhesive layer or the like, or can be positioned or arranged within the article, such as adjacent to a fixed or movable member of the article. The article may be a structure. The article may be a vehicle. The article may be a battery component or a battery such as a lithium-ion battery. For example, the coating composition of the present invention or a crosslinked self-supporting film or sheet can be applied to any structural element of a battery, in particular a lithium-ion battery, in order to obtain a battery according to the present invention. The battery may comprise an outer wall element defining a housing, and optionally an inner wall element, and the crosslinked expandable coating or crosslinked expandable self-supporting film or sheet is applied at least partially to the outside and / or inside of any of the outer wall elements, and / or any side of any of the inner wall elements, if present. The outer and / or inner wall elements may include, for example, composite materials, steel, aluminum, and / or polycarbonate. This coating composition may be particularly suitable for use in batteries because it forms a strong carbon with relatively little expansion, making it suitable for the limited gap space between the battery module and the case.

[0077] Batteries, particularly lithium-ion batteries, can be battery packs comprising multiple individual battery cells, and the coating or crosslinked expandable self-supporting film or sheet is positioned to thermally insulate at least some of the individual battery cells from each other, such as between two battery cells, in an expanded and, if necessary, carbonized state. In addition, the curable expandable coating composition or the crosslinked expandable self-supporting film or sheet can be applied or positioned adjacent to the housing walls and internal divider walls of the battery pack, as discussed above.

[0078] It may be desirable to use one or more additional flame-retardant materials and / or fire-mitigating measures within and / or around the battery. For example, thermal insulating materials or high-strength materials may be wrapped around or otherwise positioned between battery cells, or around or inside the battery housing. Examples of such materials include glass fiber, mineral wool, silica / silica fiber, alumina, Kevlar, Nomex, calcium silicate, or calcium silicate fiber, which may be, for example, sheets or other self-supporting forms. Foams such as polyurethane / polyurea foam can also be used together with flame retardants. Physical barriers such as cooling fins sandwiched between battery cells, mica boards, aerogel blankets, and / or mineral / glass / carbon fiber-containing blankets can also be used.

[0079] To provide fire protection for articles containing batteries and their users, the present invention also includes applying a curable expandable coating composition or a crosslinked expandable self-supporting film or sheet to a portion of the article adjacent to the battery between the battery and the article, thereby insulating the article from the battery. In such cases, conventional batteries or batteries according to the present invention can be used. The article may be, for example, a mobile phone, a tablet, or a laptop computer.

[0080] Alternatively, the article may be a vehicle such as a hybrid or electric car, bus, or truck. In such a vehicle, it is common to position the battery, particularly a lithium-ion battery, as a flat battery pack beneath the vehicle body, for example, the floor portion of the vehicle body, due to the weight of the battery. In such cases, the coating or crosslinked expandable self-supporting film or sheet of the present invention can be applied to the vehicle floor portion adjacent to the battery, between the battery and the vehicle body. This would protect the vehicle body, particularly the passenger cabin, from the spread of fire to the passenger cabin in the event of a battery thermal runaway or battery fire, and would limit the temperature rise of the passenger cabin over a long period of time, giving passengers sufficient time to safely escape the vehicle in the event of such an event.

[0081] The compositions of the present invention can be applied by any standard means in the art, including electrocoating, spray coating, electrostatic spray coating, dipping, rolling, and brushing, including robotic application.

[0082] Where used herein, unless otherwise explicitly specified, all numbers, including those representing values, ranges, quantities, or percentages, can be read as if preceded by the word “approximately,” even if the term does not explicitly appear. Furthermore, any numerical range described herein is intended to include all subranges belonging thereto. The singular form encompasses the plural form, and vice versa. For example, where herein we refer to “a (a)” film-forming component, “a (a)” film-forming resin, “a (a)” phosphate source, “a (a)” borate source, “a (a)” silica source, “a (an)” aluminum source, “a (a)” gas source, etc., but one or more of each of these and any other component may be used. Also, where used herein, the term “polymer” means both prepolymers, oligomers, and homopolymers and copolymers, and the prefix “poly” means two or more. Where ranges are given, any endpoint of those ranges and / or any numerical value within those ranges may be combined with the range of the present invention. The terms “including,” “such as,” “for example,” and similar terms mean “not limited to, but including / such as / for example.” The terms “acrylic” and “acrylate” are used interchangeably (unless doing so changes the intended meaning) and, unless otherwise clearly indicated, include acrylic acids, anhydrides, and their derivatives, lower alkyl-substituted acrylic acids, such as C1-C2 substituted acrylic acids like methacrylic acid and ethacrylic acid, as well as their C1-C6 alkyl and hydroxyalkyl esters.

[0083] In consideration of the foregoing, this disclosure relates in particular to the following aspects, but is not limited to these:

[0084] In the first embodiment, the coating composition is a) Film-forming component, b) Phosphate source, c) At least one of a borate source, an aluminum source, and / or a silica source, d) TiO2 and, e) Gas source, including, A coating composition is disclosed in which, based on the total solid weight of the composition, TiO2 is present in an amount of 5 to 20% by weight, a phosphate source is present in an amount of 20 to 55% by weight, and if component c contains a borate source, it is present in an amount of 5 to 20% by weight, if component c contains an aluminum source, it is present in an amount of 0.1 to 10% by weight, and if component c contains a silica source, it is present in an amount of 0.1 to 5% by weight.

[0085] The second aspect relates to the coating composition according to the preceding first aspect, wherein TiO2 is present in an amount of 9 to 15% by weight based on the total solid weight of the composition.

[0086] A third aspect relates to a coating composition according to either the preceding first or second aspect, wherein the phosphate source is present in an amount of 25 to 40% by weight.

[0087] A fourth aspect relates to a coating composition according to either the preceding first or second aspect, wherein the phosphate source is present in an amount of 40 to 55% by weight based on the total solid weight of the composition.

[0088] The fifth aspect relates to a coating composition according to any one of the preceding first to fourth aspects, wherein component c comprises a borate source, the borate source is present in an amount preferably 9 to 15% by weight based on the total solid weight of the composition.

[0089] The sixth aspect relates to a coating composition according to any one of the preceding first to fifth aspects, wherein component c comprises an aluminum source, and the aluminum source is present in an amount preferably 0.2 to 8% by weight based on the total solid weight of the composition.

[0090] The seventh aspect relates to a coating composition according to any one of the preceding first to sixth aspects, wherein component c comprises a silica source, and the silica source is present in an amount preferably 0.4 to 1% by weight based on the total solid weight of the composition.

[0091] The eighth aspect relates to a coating composition according to any one of the preceding first to seventh aspects, wherein the film-forming component is present in an amount of 20 to 60% by weight based on the total solid weight of the composition.

[0092] The ninth aspect relates to a coating composition according to any one of the preceding first to eighth aspects, wherein the gas source is present in an amount of 1 to 10% by weight, based on the total solid weight of the composition.

[0093] The tenth aspect relates to a coating composition according to any one of the preceding first to ninth aspects, wherein the coating composition further comprises fibers such as glass fibers and / or mineral fibers in an amount of up to 4% by weight, based on the total solid weight of the composition.

[0094] The eleventh aspect relates to a coating composition according to any one of the preceding first to tenth aspects, wherein the coating composition further comprises one or more additives in a total amount of 2 to 20% by weight, based on the total solid weight of the composition.

[0095] The twelfth aspect relates to a coating composition according to any one of the preceding first to eleventh aspects, wherein the film-forming component comprises a film-forming resin and, optionally, a crosslinking agent such as an epoxy resin and an amine crosslinking agent.

[0096] The thirteenth aspect relates to a coating composition according to any one of the preceding first to twelfth aspects, wherein the phosphate source comprises ammonium phosphate, triphenyl phosphate, and / or tri(2-chloroisopropyl) phosphate, preferably ammonium polyphosphate.

[0097] The 14th aspect relates to a coating composition according to any one of the 1st to 13th aspects, wherein the borate source, if used, comprises a metallic borate ammonium pentaborate and / or boric acid.

[0098] The 15th aspect relates to a coating composition according to any one of the preceding 1 to 14 aspects, wherein the aluminum source, when used, comprises aluminum hydroxide and / or aluminum oxide.

[0099] The sixteenth aspect relates to a coating composition according to any one of the preceding first to fifteenth aspects, wherein the silica source, if used, includes fumed silica.

[0100] The 17th aspect relates to a coating composition according to any one of the preceding 1 to 16 aspects, wherein the gas source comprises melamine, urea, and / or expandable graphite.

[0101] The 18th aspect relates to a self-supporting film or sheet formed from a coating composition according to any one of the preceding 1st to 17th aspects.

[0102] In the 19th aspect, a method for coating a substrate is further disclosed, which includes applying a coating composition described in any one of the preceding 1 to 17 aspects, or a film or sheet described in the preceding 18th aspect, to at least a portion of the substrate.

[0103] The 20th aspect relates to the method of the preceding 19th aspect, wherein the substrate includes a metal such as aluminum or steel, or a plastic such as polycarbonate.

[0104] In the 21st aspect, a substrate coated according to the method described in the preceding 19th or 20th aspect is disclosed.

[0105] The 22nd aspect further relates to an article comprising the base material described in the preceding 21st aspect.

[0106] The 23rd aspect relates to an article described in the preceding 22nd aspect, wherein the article includes a vehicle or a structure.

[0107] The 24th aspect relates to the article described in the preceding 22nd aspect, wherein the article includes a lithium-ion battery.

[0108] The 25th aspect relates to the article according to the preceding 24th aspect, wherein the battery comprises an outer wall element defining a housing, and optionally an inner wall element, and a coating composition or film or sheet is applied at least partially to any outer and / or inner side of any of the outer wall elements, and / or any of the inner wall elements, if present.

[0109] The 26th aspect relates to the article described in the preceding 25th aspect, wherein either the exterior wall element and / or the interior wall element includes a composite material, steel, aluminum, and / or polycarbonate.

[0110] The 27th aspect relates to an article according to any one of the preceding 24th to 26th aspects, wherein the battery is a battery pack comprising a plurality of individual battery cells, and the coating composition or film or sheet is positioned to thermally insulate at least two of the individual battery cells from each other in an expanded and optionally carbonized state, and the battery optionally includes one or more additional flame retardant materials and / or fire mitigation means.

[0111] In the 28th aspect, a battery component is disclosed which is at least partially coated with a coating composition described in any one of the preceding 1 to 17 aspects, or to which a film or sheet described in the preceding 18th aspect is applied.

[0112] The 29th aspect relates to a battery component as described in the preceding 28th aspect, wherein the battery component includes a battery component for an electric vehicle.

[0113] Further embodiments relate to battery components described in any one of the preceding 28th or 29th embodiments, wherein the battery components include battery cells, battery shells, battery modules, battery packs, battery boxes, battery cell casings, pack shells, battery covers and trays, thermal management systems, battery housings, module housings, module racking, battery side plates, battery cell housings, cooling modules, cooling tubes, cooling fins, cooling plates, busbars, battery frames, electrical connections, metal wires, copper or aluminum conductors or cables, or any combination thereof. [Examples]

[0114] The following examples are intended to illustrate the present invention and should not be construed as limiting the invention in any way.

[0115] Examples Numerous coating formulations (Formulations 1-13) were prepared using the following components. A base for each coating formulation was prepared by dispersing all components under a high-speed dispersion machine until the particle size in the formulation was less than 100 microns. A hardener for each coating formulation was prepared by dispersing all components under a high-speed dispersion machine until the particle size in the formulation was less than 100 microns. The dispersion speed and disperser plate size were 2000 rpm and 80 mm, respectively, for a 180 mm container diameter. Immediately before application, the base and hardener were mixed in the relative amounts shown in the table below. The base and hardener were mixed with a mixer or spatula until the mixture was homogeneous in color and free of lumps. Each coating formulation was applied to a 150 × 75 × 1.2 mm aluminum panel using airless spray application. The resulting coatings were then tested for 10 minutes against a torch flame at 1200 ± 50°C using a gas pressure of 2 bar and a burner diameter of 30 mm. The temperature of the back surface of the aluminum panel was monitored. The coefficient of thermal expansion of the coating, defined as the ratio between the thickness of the expanded coating and the thickness of the virgin coating, and the adhesion to the formed char and substrate were evaluated. The results are summarized in Table 1 below. [Table 1] [Table 2] [Table 3] [Table 4] [Table 5] [Table 6] [Table 7] Table 8 Table 9 Table 10 Table 11 Table 12 Table 13 Table 14 Table 15 Table 16 Table 17 Table 18 Table 19 Table 20 Table 21 Table 22 Table 23 Table 24 Table 25 [Table 26] [Table 27-1] [Table 27-2] [Table 27-3]

[0116] As can be seen from the results above, formulation 1, which contains borate but lacks TiO2 and has an APP of less than 20 wt%, did not expand sufficiently and yielded unacceptable charcoal that did not adhere to the substrate after expansion. Similar results were observed for formulations 2, 3, and 4, which used less than 5 wt% TiO2 and / or less than 20 wt% APP. The charcoal in these formulations did not expand properly, no charcoal residue was observed on the exposed substrate, and the charcoal showed insufficient substrate adhesion. Formulation 8, which contains TiO2 but lacks borate, also showed excessive expansion, resulting in low charcoal density and, consequently, the unacceptable result of the charcoal layer being removed by torch flame blowing. Formulations 5, 6, and 7, which, based on total solid weight, had TiO2 and borate amounts in the range of 5-20 wt% and an APP in the range of 20-55 wt%, yielded both acceptable charcoal and acceptable adhesion, even with a torch diameter of 15 mm and a flame blowing pressure of 2 bar. A clear example of "good adhesion" can be seen in the second photograph of formulation 6, where a cross-section of the char is shown, and the char is dense and clear delamination from the substrate is visible. Acceptable char and adhesion results were also obtained in formulations 9-13 having the stated amounts of TiO2, APP, aluminum source, and / or silica source.

[0117] While specific examples of the present invention have been described above for illustrative purposes, it will be apparent to those skilled in the art that numerous modifications can be made to the details of the invention without departing from the invention as defined in the appended claims. For example, the present invention provides the following items: (Item 1) The present invention relates to a coating composition, a) Film-forming component, b) Phosphate source, c) Borate source, aluminum source, and / or silica source, d)TiO 2 and, e) Gas source, including, The TiO 2 The present invention relates to a coating composition in which component c is present in an amount of 5 to 20% by weight, such as 9 to 15% by weight, the phosphate source is present in an amount of 20 to 55% by weight, such as 25 to 40% by weight or 40 to 55% by weight, and if component c contains a borate source, it is present in an amount of 5 to 20% by weight, such as 9 to 15% by weight, if component c contains an aluminum source, it is present in an amount of 0.1 to 10% by weight, such as 0.2 to 8% by weight, and if component c contains a silica source, it is present in an amount of 0.1 to 5% by weight, such as 0.4 to 1% by weight. (Item 2) The coating composition according to item 1, wherein the film-forming component is present in an amount of 20 to 60% by weight, based on the total solid weight of the composition, and / or the gas source is present in an amount of 1 to 10% by weight. (Item 3) The coating composition according to any one of the preceding items, further comprising, in weight percent based on the total solid weight of the composition, up to 4% by weight of fibers such as glass fibers and / or mineral fibers. (Item 4) The coating composition according to any one of the preceding items, further comprising one or more additives in a total amount of 2 to 20% by weight, based on the total solid weight of the composition. (Item 5) The coating composition according to any one of the preceding items, wherein the film-forming component comprises an epoxy resin and an amine crosslinking agent, the phosphate source comprises ammonium phosphate, triphenyl phosphate, and / or tri(2-chloroisopropyl) phosphate, the borate source, if used, comprises a metal borate, ammonium pentaborate, and / or boric acid, the gas source comprises melamine, urea, and / or expandable graphite, the aluminum source, if used, comprises aluminum hydroxide and / or aluminum oxide, and the silica source, if used, comprises fumed silica. (Item 6) A self-supporting film or sheet formed from a coating composition described in any one of the preceding items. (Item 7) A method for coating a substrate, comprising applying a coating composition according to any one of items 1 to 5, or a film or sheet according to item 6, to at least a portion of the substrate. (Item 8) The method according to item 7, wherein the substrate includes a metal such as aluminum or steel, or a plastic such as polycarbonate. (Item 9) A substrate coated according to the method described in either item 7 or 8. (Item 10) An article comprising the base material described in item 9. (Item 11) The article described in item 10, wherein the article includes a lithium-ion battery. (Item 12) The article according to item 11, wherein the battery comprises an outer wall element defining a housing, and optionally an inner wall element, and the coating composition or film or sheet is applied at least partially to any outer and / or inner side of any of the outer wall elements, and / or, if present, to any of the inner wall elements. (Item 13) The article described in item 12, wherein either of the exterior wall elements and / or interior wall elements includes composite material, steel, aluminum, and / or polycarbonate. (Item 14) The article according to any one of items 11 to 13, wherein the battery is a battery pack comprising a plurality of individual battery cells, wherein the coating composition or film or sheet is positioned to thermally insulate at least two of the individual battery cells from each other in an expanded and optionally carbonized state, and the battery optionally comprises one or more additional flame retardant materials and / or fire mitigation means. (Item 15) The articles mentioned above include vehicles, as specified in item 10. (Item 16) The article described in item 10, wherein the article includes a structure. (Item 17) The article according to item 10, wherein the article is a battery component that is at least partially coated with a coating composition according to any one of items 1 to 5, or a battery component to which a film or sheet according to item 6 is applied. (Item 18) The battery component described in item 17, wherein the battery component includes a battery component for an electric vehicle. (Item 19) The battery components described in item 17 or 18 include battery cells, battery shells, battery modules, battery packs, battery boxes, battery cell casings, pack shells, battery covers and trays, thermal management systems, battery housings, module housings, module racking, battery side plates, battery cell housings, cooling modules, cooling tubes, cooling fins, cooling plates, busbars, battery frames, electrical connections, metal wires, copper or aluminum conductors or cables, or any combination thereof.

Claims

1. A coating composition for use in batteries, a) A film-forming component comprising epoxy resin and amine crosslinking agent, b) Phosphate source, c) Borate source and d) TiO ２ and, e) Gas source, including, The TiO ２ A coating composition comprising the presence of 5 to 20% by weight of the phosphate source, the presence of 20 to 55% by weight of the borate source, and the presence of 5 to 20% by weight of the borate source.

2. The coating composition according to claim 1, further comprising an aluminum source and / or a silica source, wherein the aluminum source is present in an amount of 0.1 to 10% by weight and the silica source is present in an amount of 0.1 to 5% by weight, based on the total solid weight of the composition.

3. The coating composition according to claim 1 or 2, wherein the film-forming component is present in an amount of 20 to 60% by weight, based on the total solid weight of the composition, and / or the gas source is present in an amount of 1 to 10% by weight.

4. The coating composition according to any one of claims 1 to 3, further comprising fibers in a weight percentage based on the total solid weight of the composition, in an amount of up to 4% by weight.

5. The coating composition according to any one of claims 1 to 3, further comprising one or more additives in a total amount of 2 to 20% by weight, based on the total solid weight of the composition.

6. The coating composition according to any one of claims 1 to 5, wherein the phosphate source comprises ammonium phosphate, triphenyl phosphate, and / or tri(2-chloroisopropyl) phosphate; the borate source, if used, comprises a borate metal salt, ammonium pentaborate, and / or boric acid; the gas source comprises melamine, urea, and / or expandable graphite; the aluminum source, if used, comprises aluminum hydroxide and / or aluminum oxide; and the silica source, if used, comprises fumed silica.

7. A self-supporting film or sheet formed from the coating composition according to any one of claims 1 to 6.

8. A method for coating a substrate, comprising applying a coating composition according to any one of claims 1 to 6, or a film or sheet according to claim 7, to at least a portion of the substrate.

9. The method according to claim 8, wherein the substrate includes metal or plastic.

10. A substrate coated according to the method described in any one of claims 8 or 9.

11. An article comprising the base material described in claim 10.

12. The article according to claim 11, wherein the article includes a lithium-ion battery.

13. The article according to claim 12, wherein the battery comprises an outer wall element defining a housing, and optionally an inner wall element, and the coating composition or film or sheet is applied at least partially to any outer and / or inner side of any of the outer wall elements, and / or, if present, to any of the inner wall elements.

14. The article according to claim 13, wherein either of the exterior wall element and / or interior wall element comprises steel, aluminum, and / or polycarbonate.

15. The article according to any one of claims 12 to 14, wherein the battery is a battery pack comprising a plurality of individual battery cells, the coating composition or film or sheet is positioned to thermally insulate at least two of the individual battery cells from each other in an expanded and optionally carbonized state, and the battery optionally comprises one or more additional flame retardant materials and / or fire mitigation means.

16. The article according to claim 11, wherein the article includes a vehicle.

17. The article according to claim 11, wherein the article includes a structure.

18. The article according to claim 11, wherein the article is a battery component at least partially coated with the coating composition described in any one of claims 1 to 6, or a battery component to which the film or sheet described in claim 7 is applied.

19. The battery component according to claim 18, wherein the battery component includes a battery component for an electric vehicle.

20. The battery component according to claim 18 or 19, wherein the battery component includes a battery cell, a battery shell, a battery module, a battery pack, a battery box, a battery cell casing, a pack shell, a battery cover and tray, a thermal management system, a battery housing, a module housing, a module racking, a battery side plate, a battery cell housing, a cooling module, a cooling tube, a cooling fin, a cooling plate, a busbar, a battery frame, electrical connections, metal wires, a copper or aluminum conductor or cable, or any combination thereof.

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