Coil coating compositions and methods of use

Abstract

A coating composition that includes components containing a urethane (meth)acrylate oligomer and a monomeric (meth)acrylate ester. The components can be cured when exposed to actinic radiation and / or ionizing radiation. The coating composition can have a flow time of from 40 to 180 seconds determined using a 4 mm Din Flow Cup determined according to DIN 53211 (1987) at 25 °C, or a viscosity of from 100 to 1,000 cSt determined using a Brookfield RV viscometer using spindle no. 6 at 10 rpm and 25 °C according to ASTM : D 2196 – 99. The coating composition can be used in coil coating applications resulting in a coated coil.

Description

COIL COATING COMPOSITIONS AND METHODS OF USECROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority of prior U.S. Provisional Application Serial No. 63 / 701,103, filed September 30, 2024, titled “COIL COATING COMPOSITIONS AND METHODS OF USE”, which is incorporated herein by reference.FIELD

[0002] This disclosure generally relates to coating compositions that can be used, as a nonlimiting example, to coat metal sheets and / or coils, methods of coating such metal sheets and / or coils and the resulting coated metal sheets and / or coils.BACKGROUND

[0003] Coil coating is typically a continuous, automated process for coating metal before fabrication into end products. The metal substrate can be delivered in coil form from, as a nonlimiting example, a rolling mill. The metal coil is positioned at the beginning of the coil coating line, and in one continuous process, the coil is unwound, optionally pre-cleaned, optionally pretreated, optionally primed, and the coating applied before being recoiled on the other end of the coil coating line and packaged for shipment. The product obtained by this process is a pre-coated metal. The pre-coated metal can be used, as nonlimiting examples, in construction applications as well as appliances.SUMMARY

[0004] The present disclosure is directed to a coating composition, that includes components containing a urethane (meth)acrylate oligomer and a monomeric (meth)acrylate ester. The components can be cured when exposed to actinic radiation and / or ionizing radiation. The coating composition can have a flow time of from 40 to 180 seconds determined using a 4 mm Din Flow Cup determined according to DIN 53211 (1987) at 25 °C.DETAILED DESCRIPTION

[0005] For the purposes of the following detailed description, it is to be understood that the disclosure may assume various alternative variations and step sequences, except where expressly specified to the contrary. Moreover, other than in any operating examples, or where otherwiseindicated, all numbers expressing, for example, quantities of ingredients used in the specification and claims are to be understood as being modified in all instances by the term “about”. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties to be obtained by the present disclosure. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.I. Definitions

[0006] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard variation found in their respective testing measurements.

[0007] Also, it should be understood, that any numerical range recited herein is intended to include all sub-ranges subsumed therein. For example, a range of “1 to 10” is intended to include all sub-ranges between (and including) the recited minimum value of 1 and the recited maximum value of 10, that is, having a minimum value equal to or greater than 1 and a maximum value of equal to or less than 10.

[0008] In this application, the use of the singular includes the plural and plural encompasses the singular, unless specifically stated otherwise. In addition, in this application, the use of “or” means “and / or” unless specifically stated otherwise, even though “and / or” may be explicitly used in certain instances. Further, in this application, the use of “a” or “an” means “at least one” unless specifically stated otherwise. For example, “a” polymer, “an” acid, and the like refer to one or more of any of these items.

[0009] Unless otherwise indicated, ambient conditions of temperature and pressure are ambient temperature (20-25°C,such as 23°C) and standard pressure of 101.3 kPa (1 atm) at a relative humidity in the air of 35% to 75%, such as 55%.

[0010] As used herein, “actinic radiation” refers to electromagnetic radiation that can cause chemical changes in materials by breaking chemical bonds. It can include ultraviolet (UV) light, but can also include some visible and infrared wavelengths.

[0011] As used herein, the term “ASTM” refers to publications of ASTM International, West Conshohocken, PA.

[0012] As used herein, the term “aromatic” refers to an unsaturated cyclic moiety which exhibits, or is expected to exhibit, the characteristic properties of aromaticity, including but not limited to reactivity with electrophiles to form substitution product.

[0013] As used herein, the term “aromatic compound” refers to a compound comprising one or more mono- or polycyclic aromatic rings.

[0014] As used herein, the term “nuclear-substituted aromatic compound” refers to an aromatic compound in which one or more of the one or more mono- or polycyclic aromatic rings comprises a substituent.

[0015] As used herein, the terms “backbone” and “polymer backbone” refer to the main chain of monomeric repeat units making up the main chain of a polymer.

[0016] As used herein, the term “basecoat” refers to a coating layer that is applied onto a primer coat, another basecoat layer; and / or directly onto a substrate, optionally including components (such as colorants) that impact the color and / or provide other visual impact. A clearcoat may be applied over the basecoat layer.

[0017] As used herein the term “clearcoaf ’ refers to a coating layer that is at least substantially transparent, tinted or fully transparent and often does not include a colorant. The term “substantially transparent” refers to a coating, wherein a surface beyond the coating layer is at least partially visible to the naked eye when viewed through the coating. The term “fully transparent” refers to a coating, wherein a surface beyond the coating layer is completely visible to the naked eye when viewed through the coating.

[0018] As used herein, the term “coating” refers to the finished product resulting from applying one or more coating compositions to a substrate and forming the coating, as a nonlimiting example by curing. A primer coat, basecoat or color coat layer and clearcoat layer can comprise part of a coating. As used herein, the term “coating layer” is used to refer to the result of applying one or more coating compositions on a substrate in one or more applications of such one or more coating compositions. As a nonlimiting example, a single coating layer, referred to as a “color coat” or “topcoat” can be used to provide the function of both a basecoat and a clearcoat and can comprise the result of two or more applications of a color coat coating composition.

[0019] As used herein, the term “colorant” refers to any substance that imparts color and / or other opacity and / or other visual effect to a coating composition and can include, without limitation dyes and pigments.

[0020] As used herein, the transitional term “comprising” (and other comparable terms, e.g., “containing” and “including”) is “open-ended” and open to the inclusion of unspecified matter. Although described in terms of “comprising”, the terms “consisting essentially of’ and “consisting of’ are also within the scope of the disclosure.

[0021] As used herein, the terms “crosslinker” and “crosslinking agent”, used interchangeably, refers to a molecule or polymer containing functional groups that are reactive with the crosslinking-functional group of the polymers and / or resins in the coating composition.

[0022] As used herein, the term “crosslinking-functional group" and similar terms refer to functional groups that are positioned in the backbone of a polymer, often, in a group pendant from the backbone of the polymer, terminally positioned on the backbone of the polymer, or combinations thereof, wherein such functional groups are capable of reacting with other crosslinking-functional groups or separate crosslinking agents during curing to produce a crosslinked coating.

[0023] As used herein, the terms “curable”, “cure”, and the like, as used in connection with a coating composition, refer to at least a portion of the components that make up the coating composition that are polymerizable and / or crosslinkable, via a condensation or free radical reaction, when, as a nonlimiting example, exposed to higher temperatures, ultraviolet and / or ionizing radiation.

[0024] As used herein, the terms “curtain coating” and similar terms refer to a process that creates an uninterrupted curtain of fluid that falls onto a substrate. The substrate can be transported on a conveyor belt or calender rolls at a regulated speed through the curtain to ensure an even coat.

[0025] As used herein the term “difunctional monomer” refers to a monomer that contains two polymerizable olefinic groups.

[0026] As used herein, the term “dry film thickness” refers to the measurement of the thickness of a coating applied to a substrate, whether it be a single layer or multiple layers as determined according to NF EN 13523-1 (2024).

[0027] As used herein the term “dye” refers to a colored substance, in many cases an organic compound, that can chemically bond to a substrate or another component in a coating composition.

[0028] As used herein the term “electron beam radiation” refers to a non-thermal process using a stream of high-energy electrons, as ionizing radiation, to irradiate materials, providing the excitation required to initiate a curing process in a coating.

[0029] As used herein, the term “film-forming” materials refers to film-forming constituents of a coating composition and can include polymers, resins, crosslinking materials or any combination thereof that are film-forming constituents of the coating composition. Film-forming materials can be dried or cured, as nonlimiting examples, by exposure to elevated temperatures (for example, above 40°C), actinic radiation or under ambient conditions.

[0030] As used herein, the terms “gloss” or “specular gloss” refer to how well a surface reflects light in a specular (mirror-like) direction as determined according to NF EN 13523-2 (2021).

[0031] As used herein, the term “hydroxyl functional compound” and similar terms refer to an organic compound containing one or more hydroxyl (-OH) groups.

[0032] As used herein, the term “ionizing radiation” refers to radiation that has enough energy to break an electron away from an atom that is capable of initiating polymerization.

[0033] As used herein, the term “isocyanate reactive compound” refers to a molecule that includes at least one group, such as, without limitation, hydroxyl, primary or secondary amine and / or thiol, that is reactive with an isocyanate group.

[0034] As used herein, the term “matting agent” refers to a compound added to a coating composition to reduce the gloss of a surface of a coating layer formed therefrom, as compared a coating layer from a composition lacking the matting agent, by giving the surface a matte or satin finish.

[0035] As used herein, the term “(meth)acrylate” refers to a compound that includes at least one methacrylate functionality, or at least one acrylate functionality, and any combinations thereof. The term meth(acrylate) and similar terms can include multiple (meth)acrylate functionalities and / or multiple acrylate functionalities, or any combinations thereof.

[0036] Unless otherwise indicated, as used herein, the term "molecular weight" refers to a weight average molecular weight as determined by gel permeation chromatography (GPC) using appropriate polystyrene standards. If a number average molecular weight is specified, the weight is determined in the same GPC manner, while calculating a number average from the thus obtained polymer molecular weight distribution data. “Number average molecular weight” refers to the total weight of a material divided by the number of molecules in the material and can be determinedusing gel permeation chromatography. Unless otherwise noted, “weight average molecular weight”, and “number average molecular weight” are in units of Daltons (Da) or g / mol.

[0037] As used herein, the term “monocoat” refers to a coating layer, which can be a single coating layer, such as a topcoat, used to finish a surface of a substrate and not followed by the application of another coating layer, such as a clearcoat.

[0038] As used herein the term “monomer” refers to a molecule that can react together with other monomer molecules, through polymerization processes, to form a larger polymer chain or three-dimensional network.

[0039] As used herein the terms “multi component”, “multi -K” and “multi-pack” refers to a coating composition that includes a first component that contains crosslinkable resins, a second component that contains crosslinking agents and additional components that may or may not contain crosslinkable resins or crosslinking agents, where the components are maintained separately until just prior to use. The crosslinkable resins and crosslinking agents are capable of reacting when combined to form a thermoset composition. When the multi component coating composition does not include additional components, it is a two-component or 2-K coating composition.

[0040] As used herein, the terms “NF EN” and “EN” refer to NF (Norme Fran^aise) standards developed by AFNOR (Association Frangaise de Normalisation), the French standardization organization, and can be tied to the development and adoption of European standards, also known as EN standards which are technical standards created by the European Standards Organizations (ESOs).

[0041] As used herein, the term “Norrish Type I photoinitiator” refers to a compound that when irradiated with UV-light, undergoes homolytic bond cleavage, generating two highly reactive radical species capable of initiating polymerization.

[0042] As used herein, the term “olefinic group” refers to one or more pairs of carbon atoms linked by a double bond in a compound containing hydrogen and carbon.

[0043] As used herein, the term “oligomer” refers to a substance composed of molecules containing one or more species of atoms or groups of atoms repetitively linked to each other. Unless otherwise indicated, an oligomer has a number average molecular weight of less than 10,000 Daltons, such as less than 2,000 Daltons or from 500 to 5,000 Daltons. In radiation-curable coating compositions, an oligomer carries one or more polymerizable functional groups (e.g.,acrylate, methacrylate, vinyl, allyl, epoxy, thiol, or other unsaturated groups) and serves as the primary film-forming component that imparts mechanical strength, flexibility, chemical resistance, and adhesion upon curing.

[0044] As used herein the terms “one component”, “1-K” and “1-pack” refer to a coating composition where all of the coating components are maintained in the same package after manufacture, during shipping and storage and are maintained in the same container after manufacture, during storage, and the like, and may remain stable (not substantially react or gel) for longer than 1 month at conditions of 40-120°F (4-49°C) at 0-95% relative humidity, such as longer than 3 months, longer than 6 months, longer than 9 months, or longer than 12 months.

[0045] As used herein, the term “organic solvent” refers to carbon-based substances capable of dissolving or dispersing other substances at ambient conditions.

[0046] As used herein, the term “pigment” refers to a colored material, often an inorganic compound, that is completely or nearly insoluble in a solvent at ambient conditions.

[0047] As used herein, the term “polyester” refers to molecules or moi eties containing more than one ester (-C(O)-O-) containing repeat groups.

[0048] As used herein, the term “polyether” refers to organic polymers made up of monomers linked by ether linkages, which can be terminated with hydroxyl groups.

[0049] As used herein the prefix “poly” refers to two or more. As a nonlimiting example, a polyisocyanate refers to a compound that includes two or more isocyanate groups.

[0050] As used herein, the term “polyisocyanate” refers to compound having two or more isocyanate groups, such as two, three or four isocyanate groups and can include blocked (or capped) polyisocyanates as well as unblocked polyisocyanates.

[0051] As used herein, the term “polymer” includes homopolymers (formed from one monomer) and copolymers that are formed from two or more different monomers or that comprise two or more distinct repeat units.

[0052] As used herein, “polyol” refers to a compound having two or more hydroxyl groups, such as two, three or four hydroxyl groups.

[0053] As used herein, the term “primer coat” and similar terms, refer to an undercoating layer that can be applied onto a substrate in order to prepare the surface for application of a protective or decorative coating composition.

[0054] As used herein, the term “scratch resistance” refers to the ability of a coating on a substrate to resist the formation of scratches. Optionally, scratch resistance is determined according to DF EN 13523-12 (2017).

[0055] As used herein, the term “roll coating” and similar terms refers to a process that uses, as a nonlimiting example, two or three rollers to apply a coating to a flat substrate: a soft application roll, a pickup roll, and, optionally, a metering or doctor roll. The pickup roll may be a ceramic roll or a highly polished steel roll. The term “roll coating” can refer to 2-roll coating or 3-roll coating.

[0056] As used herein, the term “slot-die coating” and similar terms refer to a coating process that produces thin films where the coating composition is delivered onto the surface of a substrate through a precise coating head referred to as a slot-die. The slot-die has a high aspect ratio outlet controlling the final delivery of the coating liquid onto the substrate. This results in the continuous production of a wide layer of coated material on the substrate, with adjustable width depending on the dimensions of the slot-die outlet. Controlling the rate of coating composition deposition and the relative speed of the substrate, slot-die coating affords thin material coatings with easily controllable thicknesses in the range of 10 nanometers to hundreds of micrometers.

[0057] As used herein, the term “substrate” refers to an article surface to be coated and can refer to a coating layer has been previously disposed on an article, which is also considered a substrate.

[0058] As used herein, the term “thermosetting” means a polymer or resin that has functional groups that react with functional groups in a crosslinking agent or another polymer or molecule to form a network material, irreversibly transforming the “soft” polymer to a more rigid form. Thermosetting in many cases refers to resins that “set” irreversibly upon curing or crosslinking, wherein the polymer chains of the resins are joined together by covalent bonds. Once cured or crosslinked, a thermosetting resin will not melt upon the application of heat and is insoluble in solvents.

[0059] As used herein the term “thermoplastic” refers to polymers and resins that are not joined by covalent bonds and, thereby, can undergo liquid flow upon heating and can be soluble in certain solvents.

[0060] As used herein the term “topcoat” refers to an uppermost coating that is deposited over another coating layer, such as a basecoat, to provide a protective and / or decorative layer.

[0061] As used herein the terms “two component”, “2-K” and “2-pack” refers to a coating composition that includes a first component that contains a crosslinkable resins and a secondcomponent that contains crosslinking agents, where the first and the second components are maintained separately until just prior to use. The crosslinkable resins and crosslinking agents are capable of reacting when combined to form a thermoset composition.

[0062] As used herein, the term “urethane” refers to molecules that contain a group formed by reaction of an isocyanate containing molecule (-NCO) with an alcohol containing molecule (-OH) to form a urethane linkage (-N-C(O)-O-).

[0063] As used herein, the term “volatile” refers to materials that are readily vaporizable (have a vapor pressure of at least 1 mm Hg) under ambient and / or cure conditions.

[0064] As used herein, the phrase “wt.%” refers to weight percent.

[0065] Abbreviations used herein include, but are not limited to: CTFA = cyclic trimethylolpropane formal acrylate = (5-ethyl-l,3-dioxan-5-yl)methyl acrylate; cSt = centistoke = 10"2Stoke; Da = Dalton; g = gram; Gy = Gray; H12MDI = bis(4-isocyanatocyclohexyl)methane = 4,4’-methylene dicyclohexyl diisocyanate; HALS = hindered amine light stabilizer; HDDA = 1,6-hexanediol diacrylate; HDI = 1,6-hexam ethylene diisocyanate; IPDI = isophorone diisocyanate = 5-isocyanato-l-(isocyanatomethyl)-l,3,3-trimethylcyclohexane; in = inch; kGy = kilogray = 103Gray; kV = kilovolt = 103V; m = meter; mm = millimeter = 10’3m; min = minute; Pa.s = Pascal -second; s = second; St = Stoke; TBCH = 4- / erLbutylcyclohexyl acrylate; TMCHA = 3,3,5-trimethyl cyclohexane acrylate; TMXDI = tetramethyl xylylene diisocyanate = 1 ,3-bis(2- isocyanopropan-2-yl)benzene; TPO = 2,4,6-trimethylbenzoyl diphenylphosphine oxide; UV = ultraviolet; V = volt; W = watt.II. Coating Composition

[0066] The present disclosure is directed to a coating composition, that includes components containing a urethane (meth)acrylate oligomer and a monomeric (meth)acrylate ester. The components can be cured when exposed to actinic radiation and / or ionizing radiation. The coating composition can have a flow time of from 40 to 180 seconds determined using a 4 mm Din Flow Cup determined according to DIN 53211 (1987) at 25 °C, or a viscosity of from 100 to 1,000 cSt determined using a Brookfield RV viscometer using spindle no. 6 at 10 rpm and 25 °C according to ASTM : D 2196 - 99.a. Urethane (meth)acrylate oligomer

[0067] The urethane (meth)acrylate oligomer includes molecules that contain linked polyester and urethane moieties where the terminal ends of the molecule contain (meth)acrylate groups. The urethane (meth)acrylate oligomer can have the following structure:A-[-(E)x-(U)]y-(E)-B-A (I)

[0068] wherein each A is derived from (meth)acrylic acid or an alkyl hydroxy (meth)acrylate, each E is independently derived from a hydroxyl terminated ester or polyether, polyester, carbonate, or siloxane, U is a urethane, urea, amide, or other heteroatom-containing linkage derived from an isocyanate containing molecule, B represents a functionality such as a bond, -OP(O)(OR8)O-, -P(O)(OR8)O-, -NR8-, epoxy,, or mixture thereof, each R8is independently chosen from H and Ci-salkyl, x is from 0 to 10 and y is from 0 to 5. In structure I, ester or ether linkages connect moieties A and E and urethane linkages connect moieties U and E.

[0069] As a nonlimiting example, the urethane (meth)acrylate oligomer can be prepared by reacting a hydroxyl terminated ester or polyester with (meth)acrylic acid or an alkyl hydroxy (meth)acrylate such that the ratio of hydroxyl groups in the hydroxyl terminated ester or polyester to carbonyl groups in the (meth)acrylic acid or the alkyl hydroxy (meth)acrylate is greater than 1 : 1 to generate a (meth)acrylate ester of the ester or polyester maintaining hydroxyl functionality, or other isocyanate reactive compounds, in the reaction product. The hydroxyl functional (meth)acrylate ester is then reacted with an isocyanate containing molecule to provide a polyester- based urethane di(meth)acrylate oligomer.

[0070] The alkyl hydroxy (meth)acrylate can comprise hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, hydroxypentyl (meth)acrylate and / or hydroxyhexyl (meth)acrylate. The alkyl hydroxy (meth)acrylate can comprise a 2-hydroxy alkyl (meth)acrylate such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2- hydroxybutyl (meth)acrylate, 2-hydroxypentyl (meth)acrylate, and 2-hydroxyhexyl (meth)acrylate. The alkyl hydroxy (meth)acrylate can comprise an ro-hydroxy alkyl (meth)acrylatesuch as 2-hydroxy ethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate.

[0071] The ester can comprise molecules according to the following structure:R1-O-C(O)-(CR22)W-C(OH)R3-R4(II)

[0072] where R1can be methyl, ethyl, propyl or isopropyl, each R2can independently be hydrogen, methyl or ethyl, R3can be hydrogen, methyl or ethyl, R4can be hydrogen, methyl, ethyl, polyethylene glycol or polypropylene glycol, and w is from 1 to 10.

[0073] The polyester can comprise molecules according to the following structure:R5-O-[-C(O)-R6-]z-O-R7(III)

[0074] where R5represents a hydroxyl containing moiety containing from 1 to 5 carbons, R6represents a Ci to Cio linear or branched diradical, R7represents a hydroxyl containing moiety containing from 1 to 5 carbons, and z is from 2 to 10.

[0075] The polyether can comprise molecules according to the following structure:R5a-{O-[-CH2CH2O-]z-O-R7}4 (llla)

[0076] where R5arepresents a polyhydroxy- containing moiety containing from 1 to 5 carbons, R7represents a hydroxyl containing moiety containing from 1 to 5 carbons, and z is from 2 to 10.

[0077] The isocyanate containing molecule can comprise isocyanates known in the art. Suitable isocyanates may be aliphatic, aromatic, cycloaliphatic or heterocyclic isocyanates. Suitable aliphatic isocyanates may include trimethylene, tetramethylene, pentamethylene, hexamethylene, 1,2-propylene, 1,2-butylene, 2,3-butylene and 1,3-butylene diisocyanates; cycloalkylene compounds such as 1,3-cyclopentane, 1,4-cyclohexane, 1,2-cyclohexane diisocyanates and isophorone diisocyanates; aromatic compounds such as m-phenylene, -phenylene, 4,4'-diphenyl, 1,5-naphthalene and 1,4-naphthalene diisocyanates; aliphatic-aromatic compounds such as 4, d'diphenylene methane, 2,4- or 2,6-tolylene, or mixtures thereof, 4,4'-toluidine, tetramethyl xylylene, and xylylene diisocyanates; nu cl ear-substituted aromatic compounds such as dianisidine diisocyanate, 4,4'-diphenylether diisocyanate and chlorodiphenylene diisocyanate; triisocyanates such as triphenyl methane-4,4',4"-triisocyanate, 1,3,5-triisocyanato benzene, hexamethylene diisocyanate isocyanurate trimer, and 2,4,6-triisocyanato toluene; and tetraisocyanates such as4,4'-dimethyldiphenyl methane-2,2',5,5'-tetraisocyanate; polymerized polyisocyanates such as tolylene diisocyanate dimers and trimers, and the like.

[0078] Suitable diisocyanates also include diisocyanates having a single aromatic or cycloaliphatic ring such as isophorone diisocyanate (IPDI), tetramethyl xylylene diisocyanate (TMXDI), 4,4’-methylene dicyclohexyl diisocyanate (H12MDI), 1,6-hexam ethylene diisocyanate (HDI), l,3-bis(isocyanato methyl)cyclohexane, l,5-diisocyanato-2-methylpentane, 1,6- diisocyanato-2,2,4-trimethylhexane, l,6-diisocyanato-2,4,4-trimethylhexane, 1,4- diisocyanatobutanone, tri-methyl -hexamethylene diisocyanate, 1,8-diisocyanatooctane, 1,12- diisocyanatododecane, l,8-diisocyanto-2,4-dimethyloctane, l,4-bis(isocyanato methyl)cyclohexane, trans- 1,4-cyclohexylene diisocyanate, and 2,4-diisocyanato-l-methyl cyclohexane.

[0079] Other suitable aliphatic diisocyanates may also include, methyl-2,6- diisocyanatohexanoate, bis(isocyanatomethyl)cyclohexane, 1,3- bis(isocyanatomethyl)cyclohexane, 2,5(6)-bis(isocyanatomethyl)cyclo[2.2. l]heptane, 1,3,3- trimethyl-1 -(isocyanatom ethyl)-5-isocyanatocyclohexane, octahydro-4,7-methano-177- indenedimethyl diisocyanate, and l,l’-methylenebis(4-isocyanatocyclohexane).

[0080] The urethane (meth)acrylate oligomer may have a number average molecular weight (Mn) of from 500 or from 1000 to 2000 or to 1500 Da or within any range using any two of the foregoing values as endpoints, such as from 500 to 2000, or from 1000 to 2000, as determined by gel permeation chromatography using polystyrene standards.

[0081] The variables outlined above associated with the urethane (meth)acrylate oligomer are selected such that the urethane (meth)acrylate oligomer has a viscosity of less than 100 Pa.s at 25 °C, D=25 S-l according to DIN EN 12092 (2001).

[0082] The urethane (meth)acrylate oligomer can be present in the coating composition at from 10 to 40 wt.%, or from 15 to 35 wt.% based on the weight of the coating composition. b. Monomeric (meth)acrylate ester

[0083] The term monomeric (meth)acrylate ester refers to a low molecular weight (meth)acrylate ester, such as a (meth)acrylate ester having a number average molecular weight <500Da) distinct from the urethane (meth)acrylate oligomer described above and includes molecules having the following structure:A-[-(S-U)n-]P-S-A (IV)

[0084] where each A is independently derived from (meth)acrylates as described above, each S is independently derived from a hydroxyl terminated ester, a polyol and / or a polyether, a carbonate, a siloxane, or combinations thereof, each U is a urethane group derived from an isocyanate containing molecule as described above, n is from 1 to 10 and p is from 0 to 5. In structure II, ester or ether linkages connect moieties A and S and urethane linkages connect moieties U and S.

[0085] The ester, S, can comprise molecules according to the following structure:R5-O-C(O)-R6-O-R7(V)

[0086] where R5, R6and R7are as described above.

[0087] The monomeric (meth)acrylate ester may have a number average molecular weight (Mn) of from 100 or from 500 to 2000 or to 1500 Da or within any range using any two of the foregoing values as endpoints, such as from 100 to 2000 Da, or from 500 to 2000 Da, as determined by gel permeation chromatography using polystyrene standards.

[0088] The variables outlined above associated with the monomeric (meth)acrylate ester are selected such that the monomeric (meth)acrylate ester has a viscosity of less than 100 Pa.s at 25 °C, D=25 S-l according to DIN EN 12092 (2001).

[0089] The monomeric (meth)acrylate ester can be present in the coating composition at from 0 to 5 wt.% or from 0.1 to 5 wt.% based on the weight of the coating composition. c. Monofunctional monomer

[0090] When included in the coating composition according to this disclosure, the monofunctional monomer can act as a reactive diluent. Nonlimiting examples of monofunctional monomers that can be used in the coating composition according to this disclosure include (meth)acrylate ester, nonlimiting examples of which include C1-C20, linear, branched, cyclic and aromatic containing esters including those containing hetero atoms such as O, N and S. The monofunctional monomers can include methyl (meth)acrylate, ethyl (meth)acrylate, cyclohexyl (meth)acrylate and cyclic trimethylolpropane formal (meth)acrylate (“CTFA”; (5-ethyl-l,3- dioxan-5-yl)methyl acrylate). Additional suitable monofunctional monomers include vinyl ethers, allyl ethers, styrene, acrylamides and N-vinylpyrrolidone.

[0091] The monofunctional monomer can be present in the coating composition at from 25 to 80 wt.% or from 30 to 75 wt.% based on the weight of the coating composition. d. Difunctional monomer

[0092] When included in the coating composition according to this disclosure, the difunctional monomer can act as a reactive diluent. Nonlimiting examples of difunctional monomers that can be used in the coating composition according to this disclosure include 1,6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 3-methyl-l,5-pentanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, and / or diethylene glycol di(meth)acrylate.

[0093] The difunctional monomer can be present in the coating composition at from 0 to 10 w.% or from 1 to 10 wt.% based on the weight of the coating composition. e. Matting agent

[0094] The coating composition according to this disclosure can include matting agents that are used to provide a relatively rough surface to the cured coating layer. The surface of the cured coating layer is able to scatter incident light resulting in reduced gloss of the coating layer. Organic and inorganic matting agents can be used in the coating composition according to this disclosure to the extent that the viscosity of the coating composition remains within a desirable range as described herein. i. Organic matting agents

[0095] The coating composition according to this disclosure, can include an organic matting agent, which, as nonlimiting examples can include, poly (methyl urea), urea- formaldehyde resins, polystyrene and styrene-acrylic powders, polyamide powders and beads, acrylic microspheres, polyethylene wax, Fischer-Tropsch wax, carnauba wax, and wax blends, which can be micronized, for example to a size of 100 pm or smaller, or 50 pm or smaller, or 20 pm or smaller, stearic acid metal salts, where the metal can be calcium, zinc, zirconium or magnesium, mono-functional Cs- C20 alkyl (meth)acrylates, zirconium ethyl hexanoate, thermoplastic polymers and / or thermoset polymers different from the urethane (meth)acrylate oligomer or the monomeric (meth)acrylate ester, and others known in the art.

[0096] The organic matting agent can be present in the coating composition at from 0 to 20 w.% or from 1 to 15 wt.% based on the weight of the coating composition. ii. Inorganic matting agents

[0097] The coating composition according to this disclosure, can optionally include an inorganic matting agent that can include talc, silicate, including but not limited to mica, Al(OH)s, BaSC , silicas and / or inorganic oxides such as those comprising SiCh, AI2O3, AIPO4, MgO, TiCh, ZrCh, Fe20s.

[0098] The inorganic matting agent can be present in the coating composition at from 0 to 5 wt.% or from 0.1 to 4 wt.% based on the weight of the coating composition.

[0099] When not intentionally added to the coating composition according to this disclosure, the coating composition is essentially free (less than 1 wt.%), substantially free (less than 0.1 wt.%) or completely free (undetectable by FTIR) of inorganic matting agents. f. Colorants

[0100] Colorants are optionally added to the coating composition to provide aesthetic properties to the resulting cured coating as described below. The colorants can include pigments and / or dyes and can be present in the coating composition at from 0 to 50 wt.% or from 1 to 50 wt.% based on the weight of the coating composition. The colorants can include brush block copolymer colorants.

[0101] When no colorant is added, the coating composition is considered to be a clearcoat. i. Pigments

[0102] The coating composition according to this disclosure, can include pigments, which as nonlimiting examples, include organic and / or inorganic materials, non-treated aluminum, treated aluminums (with silica, inorganic pigments and / or organic pigments), titanium dioxide, zinc oxide, iron oxide, carbon black, carbazole dioxazine crude pigment, azo, monoazo, disazo, naphthol AS, salt type (lakes), benzimidazolone, metal complex, isoindolinone, isoindoline and polycyclic phthalocyanine, quinacridone, perylene, perinone, diketopyrrolo pyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone, di oxazine, tri arylcarbonium, quinophthalone pigments, diketo pyrrolo pyrrole red (“DPPBO red”), mono azo red, red iron oxide, quinacridone maroon, transparent red oxide, cobalt blue, iron blue, iron oxide yellow, chrome titanate, titanium yellow, nickel titanate yellow, reduced and / or composite tungsten oxide, transparent yellow oxide, lead chromate yellow, bismuth vanadiumyellow, pre darkened chrome yellow, transparent red oxide chip, iron oxide red, molybdate orange, molybdate orange red, aluminum flake, radar reflective pigments, LiDAR reflective pigments, corrosion inhibiting pigments, and combinations thereof. ii. Dyes

[0103] Non-limiting examples of suitable dyes that can be used in the coating composition according to this disclosure include those that are solvent and / or aqueous based such as photochromic dyes, acid dyes, azoic dyes, basic dyes, direct dyes, disperse dyes, reactive dyes, solvent dyes, sulfur dyes, mordant dyes, nonlimiting examples including bismuth vanadate, anthraquinone, perylene, aluminum, quinacridone, thiazole, thiazine, azo, indigoid, nitro, nitroso, oxazine, phthalocyanine, quinoline, stilbene, and triphenyl methane, dioxazine carbazole violet, phthalocyanine blue, indanthrone blue, mono azo permanent orange, ferrite yellow, diarylide yellow, indolinone yellow, monoazo yellow, benzimidazolone yellow, isoindoline yellow, tetrachloroisoindoline yellow, disazo yellow, anthanthrone orange, quinacridone orange, benzimidazolone orange, phthalocyanine green, quinacridone red, azoic red, di ketopyrrol opyrrole red, perylene red, scarlet or maroon, quinacridone violet, thioindigo red, and combinations thereof. g. Photoinitiator

[0104] The coating composition according to this disclosure can include a photoinitiator. Suitable photoinitiators include Norrish Type I photoinitiators.

[0105] Nonlimiting examples of suitable photoinitiators are those that will initiate polymerization in the coating composition when the coating composition is exposed to actinic radiation as described herein. Nonlimiting examples of suitable photoinitiator compounds include those containing carbonyl and / or phosphine oxide groups adjacent to one or more aromatic rings. The photoinitiator can include 1 -hydroxy cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-l- phenyl-propan-l-one, 2,4,6-trimethyl-benzyl-diphenylphosphine oxide, and / or bis(2,4,6- trimethylbenzoyljphenylphosphine oxide.

[0106] The photoinitiator can be present in the coating composition at from 0 to 5 wt.%, such as from 0.2 to 5 wt.%, or from 0.3 to 5 wt.%, or from 0 to 3 wt .%, or from 0.2 to 3 wt.%, or from 0.3 to 3 wt.% based on the weight of the coating composition.h. Volatile Organic Compounds

[0107] The coating composition according to this disclosure will often not include separately added volatile organic compounds (VOCs). However, VOCs can be introduced to the coating composition as a constituent in the other components described above. When present in the coating composition, VOCs comprise less than 5 wt.%, or less than 3 wt.% of the coating composition. i. Other components

[0108] The coating composition according to the present disclosure can include organic solvents or water added as part of other components outlined above. However, water or organic solvents are not typically added separately to the coating composition and are included at less than 5 wt.% or less than 3 wt.% based on the weight of the coating composition.

[0109] The coating composition disclosed herein can include other components, that can include, without limitation, drying agents; transparent and opaque, organic and inorganic fillers and nanoparticles; air and oxidative drying alkyd resins, UV absorbers; light stabilizers, such as HALS; radical scavengers, oxygen scavengers, including but not limited to triphenyl phosphite; anti-oxidant; slip additives; polymerization inhibitors; defoamers; emulsifiers and wetting agents; adhesion promoters; leveling agents; UV cure catalysts, including but not limited to amine catalysts, thiol catalysts, and synergist catalysts; flow agents; viscosity modifiers; foam control agents; adhesion promoters; coalescing agents; rheology-controlling additives; thermal initiators and flame retardants. The other components can individually or collectively be included in the coating composition at from 0 to 20 wt.% or from 1 to 18 wt.% or from 1 to 15 wt.% based on the weight of the coating composition. j. Liquid at ambient conditions

[0110] The coating composition according to this disclosure is a liquid at ambient and at use conditions (described below) enabling it to be applied as a coating to a substrate. As used herein, liquid at ambient conditions refers to the coating composition can have a flow time of from 40 to 180 seconds, such as from 40 to 80 seconds determined using a 4 mm Din Flow Cup determined according to DIN 53211 (1987) at 25 °C, or a viscosity of from 100 to 1,000 cSt determined using a Brookfield RV viscometer using spindle no. 6 at 10 rpm and 25 °C according to ASTM : D 2196 - 99.k. Actinic Radiation[0U1] The actinic radiation used in the present disclosure includes electromagnetic radiation capable of initiating photochemical reactions, as nonlimiting examples, UVB and UVC radiation (180-315 nm) and near-UV radiant energy in the 320-380 nm (or 400 nm) range. The actinic radiation can be used to control the gloss of the cured coating layer.

[0112] The amount of actinic radiation applied to the coating composition is an amount sufficient to at least partially cure the coating composition.

[0113] The amount of actinic radiation applied to the coating composition can be an amount ranging from 200 mJ / cm2to 3,000 mJ / cm2, or from 250 mJ / cm2to 2,500 mJ / cm2or from 300 mJ / cm2to 2,000 mJ / cm2. l. Ionizing Radiation

[0114] The ionizing radiation used in the present disclosure includes high-energy radiation, including, but not limited to gamma rays, X-rays, and / or electron beams that can be used to initiate a polymerization reaction by creating highly reactive radicals within a mixture containing polymerizable olefinic groups, leading to the formation of a polymer chain and / or crosslinks through a chain reaction mechanism, essentially allowing for polymer synthesis and / or cure without the need for a conventional free radical initiator.

[0115] The amount of applied ionizing radiation applied to the coating composition is an amount sufficient to cure the coating composition. The amount of ionizing radiation applied to the coating composition can range from 0.1 megarads to 20 megarads, or from 1 megarad to 17 megarads, or from 2 megarads to 15 megarads. m. Coating Composition Packaging

[0116] Depending on the components in the coating composition, the coating composition can be packaged with all of the components of the coating compositions in the same package, or a 1-pack composition. When certain components can cause premature polymerization or curing of the coating composition, the potentially reactive components can be packaged separately and combined and mixed together prior to use. In this instance the coating composition is considered to be a two-component or multi-pack package.III. Method of Using

[0117] Although the coating composition according to this disclosure can be applied using various methods to various substrates known in the art, the present coating composition is particularly useful for coating metal substrates and can be applied to a substrate to form a coating layer and cured using actinic radiation and / or ionizing radiation.

[0118] When the substrate is a metal coil, the coil coating process includes the continuous application of the coating composition to the coiled metal substrate. The substrate can be a metal substrate that includes cold rolled steel, hot rolled steel, electrogalvanized steel, hot dipped galvanized steel, steel plated with zinc alloy, aluminum, aluminum alloys, zinc-aluminum alloys, aluminum plated steel, aluminum alloy plated steel, zinc / magnesium alloy, and / or zinc / magnesium / aluminum alloy.

[0119] The process typically includes the following sequential steps: a. Coil Entry

[0120] The mill finish coil is placed into a decoder for entry into the coating line after inspection. The head of the new coil is spliced into the tail of running coil. Splicing one to the other is accomplished by the utilization of an accumulation tower. The accumulation tower advances stopping the tail of the running coil at the splicing unit. Once the splice is made, the carriage is moved and the line returns to its normal running position. b. Cleaning of the Coil

[0121] After the coil exits the entry accumulation tower, it optionally enters a cleaning and rinse tank area. The cleaning tanks are designed to clean the metal. After cleaning the metal, it then passes through rinse tanks to assure that the cleaner residue is removed. If the metal is not cleaned properly, coating adhesion problems can occur. c. Chemical Pretreatment

[0122] The chemical pretreatment or conversion coat step provides a protective layer to the metal substrate. This chemical treatment is designed to react with and modify the metal to produce a surface suitable for coating and to enhance coating composition adhesion. This conversion coat also provides protection to the substrate from exterior corrosion. As the metal strip continues moving forward from the final rinse tank, it is dried and moves into the chemical coating section.The chemical treatment can be applied by passing the metal strip through a spray or dip tank, and / or a coil coater is used. After exiting the chemical coater, the metal strip moves directly into a drying oven which dries the chemical treatment and eliminates any moisture from the metal strip. d. Application of coating composition(s)

[0123] The application of coating compositions to the chemically treated metal is accomplished by passing the metal strip through one or more coating roll coaters, curtain coaters and / or slot-die coaters. As a nonlimiting example, the coating roll coater can include a series of rolls that support the applicator roll to apply the coating to the metal strip.

[0124] When roll coating is used, proper coater roll setting and speeds must be monitored for accurate application of the coating film. The correct coating film will vary, depending on the specification of each individual coating composition. Before any coating is used in the coating roll coater, it must be properly mixed to achieve the specified application viscosity.

[0125] A multiple number of coating layers can be applied to the metal strip. The first layer can be a primer coating. Coil coating primers are applied to the metal strip surface as a continuous process before any subsequent coats to aid coating adhesion while adding necessary protection against corrosion. Primer coating formulations are known in the art and can add properties which improve the coating system’s flexibility and provide a tightly bonded finish.

[0126] The methods described herein can include only applying the coating compositions described herein as a single coating or monocoat to the metal substrate.

[0127] Subsequent to the primer coating, one or more basecoats can be applied to the metal substrate. Basecoats are coatings that are applied over the primed metal surface or intermediate coatings prior the present coating composition. Basecoats can provide visual properties of color and effects. They can be designed to enhance the visual appearance of final coating.

[0128] After the primer and optional basecoats, the coating composition according to this disclosure is applied to the metal substrate. Alternatively, the coating composition can be applied to the primer prior to application of the one or more basecoats.

[0129] Finally, a topcoat, which can be a clearcoat, is applied to the metal substrate.

[0130] When multiple coating layers are applied, a tandem coating line can be used, which provides the ability to apply a primer and multiple coating layers in a single pass. Alternatively, a triple line, comprising three ovens in series, can be used.e. Curing the coating(s)

[0131] After each coating layer has been applied, the continuous metal strip then moves directly into a curing section. Separate curing sections can be used for each applied coating layer, a wet on dry approach, or one or more coating layers can be applied on top of each other and then cured, a wet on wet approach. The curing section can include curing ovens that are generally natural gas fired but may also be electric.

[0132] The oven temperatures can be set at a temperature level to achieve a metal temperature sufficient to cause the applied coating to polymerize. The basic requirements needed to cure or polymerize the coating are metal temperature and time. Oven temperature adjustments are made, taking into consideration line speed, coating composition, film thickness and metal thickness. When thermal curing is primary curing mechanism for a particular coating and the conditions are all correct, the result will be a properly cured coating.

[0133] When the coating composition according to this disclosure is cured, partial thermal curing may be utilized. The coil coating line may include an actinic radiation application section followed by an ionizing radiation section. Alternatively, curing of the coating composition may be accomplished completely with thermal curing.

[0134] The actinic radiation is applied for less than 2 seconds, or from 0.05 to 1 second or from 0.1 to 0.75 seconds delivering an amount of actinic radiation ranging from 200 mJ / cm2to 3,000 mJ / cm2, or from 250 mJ / cm2to 2,500 mJ / cm2or from 300 mJ / cm2to 2,000 mJ / cm2,as measured using a radiometer such as a Power Puck® II radiometer, available from EIT 2.0 LLC .

[0135] The ionizing radiation is applied for less than 1 seconds, or from 0.01 to 0.75 seconds or from 0.1 to 0.5 seconds, delivering an amount of ionizing radiation ranging from 0.1 megarads to 20 megarads, or from 1 megarad to 17 megarads, or from 2 megarads to 15 megarads.

[0136] The cured coating layer from the coating composition according to this disclosure can have a dry film thickness of from 0.1 micron to 100 micron, or from 2 micron to 75 micron or from 3 micron to 60 micron determined according to NY EN 13523-1 (2024). f. Cooling the Strip

[0137] The coated metal strip can move directly from the curing section(s) to a cooling section of the line, particularly when ovens are used in the curing step. The purpose of the cooling sectionis to cool the cured metal strip so recoiling of the continuous strip can be achieved. When only actinic radiation and / or ionizing radiation is used for curing, the cooling step may be eliminated. g. Recoiling the Strip

[0138] As the coated metal strip exits the cooling section, it moves directly into the exit accumulation tower and to a recoiling unit.IV. Properties of the Cured Coating

[0139] The cured coating composition according to this disclosure includes a flexible thermoset resin that demonstrates a flexibility of below 5T determined according to ASTM D D3794-22.

[0140] The cured coating composition according to this disclosure can have a T-bend of 2T with no pick-off of paint using an adhesive tape and 4T without any sign of cracking on the coating surface both according to ASTM D4145-10.

[0141] The cured coating composition can have a tape adhesion rating of 5B determined according to ASTM 3359-23.

[0142] The cured coating composition according to this disclosure has a gloss retention rating of at least 80 % after 2,000 hours QUVA determined according to ASTM 4587 (2019).

[0143] The cured coating composition according to this disclosure on the metal substrate demonstrates minimal chalk formation obtaining a score of at least 7 when determined according to ASTM D4214-07.

[0144] The cured coating composition according to this disclosure on the metal substrate demonstrates minimal fade as indicated by a loss of color calculated in Hunter AE units in accordance with ASTM D2244- 11 of less than 5 AE Hunter units.

[0145] The cured coating composition according to this disclosure on the metal substrate can demonstrate solvent resistance as demonstrated by greater than 100 double rubs as determined according to NF EN 13523-11 (2019).

[0146] The cured coating composition according to this disclosure on the metal substrate can demonstrate scratch resistance as demonstrated by greater than 2200 g determined according to NF EN 13523-12 (2007).

[0147] The present disclosure is also directed to coated substrates prepared according to and having the properties of the methods described above.V. Aspects

[0148] The following numbered clauses summarize some non-limiting aspects of the present disclosure.

[0149] 1. A coating composition, comprising components comprising a urethane (meth)acrylate oligomer and a monomeric (meth)acrylate ester; wherein the components are curable when exposed to actinic radiation and / or ionizing radiation; and wherein the composition has a flow time of from 40 to 180 seconds determined using a 4 mm Din Flow Cup determined according to DIN 53211 (1987) at 25 °C.

[0150] 2. The coating composition according to aspect 1, wherein the urethane (meth)acrylate oligomer comprises molecules that contain linked polyester and urethane moieties where the terminal ends of the molecule contain (meth)acrylate groups.

[0151] 3. The coating composition according to aspect 2, wherein the urethane (meth)acrylate oligomer has the following structure (I):A-[-(E)x-(U)-]y-(E)-B-A (I)

[0152] wherein each A is derived from (meth)acrylic acid or an alkyl hydroxy (meth)acrylate, each E is independently derived from a hydroxyl terminated ester or poly ether, polyester, carbonate, or siloxane, U is a urethane, urea, amide, or other heteroatom-containing linkage derived from an isocyanate containing molecule, B represents a functionality such as a bond, -OP(O)(OR8)O-, -OP(O)(O )O-, -NR8-, epoxy,, or mixture thereof, each R8is independently chosen from H and Ci-salkyl, x is from 0 to 10 and y is from 0 to 5, wherein ester or ether linkages connect moieties A and E in structure (I) and urethane linkages connect moi eties U and E in structure (I);

[0153] 4. The coating composition according to aspect 3, wherein the urethane (meth)acrylate oligomer is prepared by reacting a hydroxyl terminated ester or polyester with (meth)acrylic acid or an alkyl hydroxy (meth)acrylate such that the ratio of hydroxyl groups in the hydroxyl terminated ester or polyester to carbonyl groups in the (meth)acrylic acid or the alkylhydroxy (meth)acrylate is greater than 1 : 1 to generate a (meth)acrylate ester of the ester or polyester maintaining hydroxyl functionality in the reaction product and wherein the hydroxyl functional (meth)acrylate ester is then reacted with an isocyanate containing molecule to provide a polyester based urethane di(meth)acrylate oligomer.

[0154] 5. The coating composition according to either one of aspects 3 and 4, wherein the ester comprises molecules according to the following structure (II):R1-O-C(O)-(CR22)w-C(OH)R3-R4(II)

[0155] wherein R1is methyl, ethyl, propyl or isopropyl, each R2is independently hydrogen, methyl or ethyl, R3is hydrogen, methyl or ethyl, R4is hydrogen, methyl, ethyl, polyethylene glycol or polypropylene glycol, and w is from 1 to 10.

[0156] 6. The coating composition according to any one of aspects 3, 4, and 5, wherein the polyester comprises molecules according to the following structure (III):R5-O-[-C(O)-R6-]z-O-R7(III)

[0157] wherein R is a hydroxyl containing moiety containing from 1 to 5 carbons, R6is a Ci to Cio linear or branched diradical, R7is a hydroxyl containing moiety containing from 1 to 5 carbons, and z is from 2 to 10.

[0158] 7 The coating composition according to any one of aspects 3, 4, 5, and 6, wherein the isocyanate containing molecule comprises:

[0159] a diisocyanate such as trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2- butylene diisocyanate, 2,3-butylene diisocyanate and 1,3-butylene diisocyanate; and / or

[0160] a cycloalkylene diisocyanate such as 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate, 1,2-cyclohexane diisocyanate and isophorone diisocyanate; and / or

[0161] an aromatic diisocyanate such as / / / -phenylene diisocyanate, / / -phenylene diisocyanate, 4,4'-biphenyl diisocyanate, 1,5 -naphthalene diisocyanate, and 1,4-naphthalene diisocyanate; and / or

[0162] an aliphatic-aromatic diisocyanate such as 4,4'-diphenylene methane, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-toluidine diiscocyanate, tetramethyl xylylene, and xylylene diisocyanate; and / or

[0163] a nuclear-substituted aromatic diisocyanate such as dianisidine diisocyanate (4,4- dii socyanato-3, 3 -dimethoxy- 1, 1 ’biphenyl), 4,4’-oxybis(isocyanatobenzene), and chlorodiphenylene diisocyanate; and / or

[0164] a triisocyanate such as triphenyl methane-4,4',4"-triisocyanate, 1,3,5-triisocyanato benzene, hexamethylene diisocyanate isocyanurate trimer, and 2,4,6-triisocyanato toluene; and / or

[0165] a tetraisocyanate such as 4,4'-dimethyldiphenyl methane-2,2',5,5'-tetraisocyanate; polymerized polyisocyanates such as tolylene diisocyanate dimers and trimers, and the like.

[0166] 8. The coating composition according to any one of aspects 3, 4, 5, and 6, wherein the isocyanate containing molecule comprises a diisocyanate having a single aromatic or cycloaliphatic ring such as isophorone diisocyanate (IPDI), tetramethyl xylylene diisocyanate (TMXDI), 4,4’-methylene dicyclohexyl diisocyanate (H12MDI), 1,6-hexam ethylene diisocyanate (HDI), l,3-bis(isocyanato methyl)cyclohexane, l,5-diisocyanato-2-methylpentane, 1,6- diisocyanato-2,2,4-trimethylhexane, l,6-diisocyanato-2,4,4-trimethylhexane, 1,4- diisocyanatobutanone, tri-methyl-hexamethylene diisocyanate, 1,8-diisocyanatooctane, 1,12- diisocyanatododecane, l,8-diisocyanto-2,4-dimethyloctane, l,4-bis(isocyanato methyl)cyclohexane, trans- 1,4-cy cl ohexylene diisocyanate, 2,4-diisocyanato-l-methyl cyclohexane, methyl-2,6-diisocyanatohexanoate, bis(isocyanatomethyl)cyclohexane, 1,3- bis(isocyanatomethyl)cyclohexane, 2,5(6)-bis(isocyanatomethyl)cyclo[2.2. l]heptane, 1,3,3- trimethyl-1 -(isocyanatom ethyl)-5-isocyanatocyclohexane, octahydro-4, 7-methano- l / / - indenedimethyl diisocyanate, and / or l,l ’-methylenebis(4-isocyanatocyclohexane).

[0167] 9. The coating composition according to any previous aspect, wherein the urethane (meth)acrylate oligomer has a number average molecular weight (Mn) of from 500 to 2000 Da, as determined by gel permeation chromatography using polystyrene standards; and / or

[0168] wherein the urethane (meth)acrylate oligomer has a viscosity of less than 100 Pa.s at 25 °C, D=25 S- l according to DIN EN 12092 (2001).

[0169] 10. The coating composition according to any preceding aspect, comprising a urethane (meth)acrylate oligomer other than the urethane (meth)acrylate oligomer.

[0170] 11. The coating composition according to aspect 3, wherein the urethane (meth)acrylate oligomer other than the urethane (meth)acrylate oligomer comprises molecules having the following structure (IV):A-[-(S-U)n-]P-S-A (IV)

[0171] wherein each A is derived from (meth)acrylates as described above, each S is independently derived from a hydroxyl terminated ester, a polyol and / or a polyether, each U is a urethane group derived from an isocyanate containing molecule as described above, n is from 1 to 10 and p is from 0 to 5, wherein in structure IV, ester or ether linkages connect moieties A and S and urethane linkages connect moieties U and S;

[0172] 12. The coating composition according to aspect 11, wherein the ester, S, comprises molecules according to the following structure:R5-O-C(O)-R6-O-R7(V)

[0173] where R5, R6and R7are as described above.

[0174] 13. The coating composition according to any preceding aspect comprising a difunctional monomer.

[0175] 14. The coating composition of aspect 13, wherein the difunctional monomer comprises 1,6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 3-methyl-l,5-pentanediol di(meth)acrylate, dipropylene glycol di(meth)acrylate, and / or diethylene glycol di(meth)acrylate.

[0176] 15. The coating composition according to any preceding aspect, wherein the coating composition comprises less than 3 wt.% of volatile organic compounds, based on the total weight of the coating composition.

[0177] 16. The coating composition according to any preceding aspect comprising a photoinitiator.

[0178] 17. The coating composition according to aspect 16, wherein the photoinitiator comprises compounds that include carbonyl and / or phosphine oxide groups adjacent to one or more aromatic rings.

[0179] 18. The coating composition according to aspect 17, wherein the photoinitiator comprises 1 -hydroxy cyclohexyl phenyl ketone, 2-hydroxy-2-methyl-l-phenyl-propan-l-one, 2,4,6-trimethyl-benzyl-diphenylphosphine oxide, and / or bis(2,4,6- trimethylbenzoylj-phenylphosphine oxide.

[0180] 19. The coating composition according to either one of aspects 17 and 18, wherein the photoinitiator is present in the coating composition at from 0 to 5 wt.%, or from 0.2 to 5 wt.%, orfrom 0 to 3 wt.%, or from 0.3 to 5 wt.%, or from 0.3 to 3 wt.%, or from 0.2 to 3 wt.% based on the weight of the coating composition.

[0181] 20. The coating composition according to any preceding aspect comprising an organic matting agent.

[0182] 21. The coating composition according to aspect 20, wherein the organic matting agent comprises poly (methyl urea), urea- formaldehyde resins, polyamide powders and beads, polyethylene wax and / or wax blends, which can be micronized, stearic acid metal salts, wherein the metal can be calcium, zinc, zirconium or magnesium, mono-functional C8-C20 alkyl (meth)acrylates, zirconium ethyl hexanoate, thermoplastic polymers and / or thermoset polymers different than the polyester urethane (meth)acrylate oligomer or the monomeric (meth)acrylate ester.

[0183] 22. The coating composition according to any preceding aspect, wherein the coating composition is essentially free (less than 1 wt.%), substantially free (less than 0.1 wt.%) or completely free (undetectable by FTIR) of inorganic matting agents.

[0184] 23. The coating composition according to any one of aspects 1 through 21 comprising an inorganic matting agent.

[0185] 24. The coating composition according to any preceding aspect comprising a colorant comprising a pigment and / or a dye.

[0186] 25. The coating composition according to any preceding aspect comprising:A. from 15 to 35 wt.% of the urethane (meth)acrylate oligomer;B. from 0 to 5 wt.% or from 0. 1 to 5 wt.% of a urethane (meth)acrylate oligomer other than the urethane (meth)acrylate oligomer;C. from 30 to 75 wt.% of a monofunctional monomeric (meth)acrylate ester;D. from 0 to 10 w.% or from 1 to 10 wt.% of a difunctional monomer;E. from 0 to 5 wt %, or from 0 to 3 wt.% or from 0.3 to 3 wt.% of a photoinitiator, based on the weight of the coating composition;F. from 0 to 10 wt.% or from 1 to 10 wt.% of an organic matting agent; andG. from 0 to 50 wt.% or from 1 to 50 wt.% of a coloring agent.

[0187] 26. The coating composition according to any preceding aspect comprising a Norrish Type I photoinitiator.

[0188] 27. The coating composition according to any preceding aspect, wherein the ionizing radiation is applied in an amount sufficient to cure the coating composition.

[0189] 28. The coating composition according to any preceding aspect, wherein the ionizing radiation is applied in an amount ranging from 0.1 megarads to 20 megarads, or from 1 megarad to 17 megarads, or from 2 megarads to 15 megarads.

[0190] 29. The coating composition according to any preceding aspect, wherein actinic radiation is applied in an amount sufficient to cure the coating composition.

[0191] 30. The coating composition according to any preceding aspect, wherein actinic radiation is applied in an amount ranging from 200 mJ / cm2to 3,000 mJ / cm2, or from 250 mJ / cm2to 2,500 mJ / cm2or from 300 mJ / cm2to 2,000 mJ / cm2.

[0192] 31. The coating composition according to any preceding aspect, wherein the coating composition comprises less than 3 wt.% of organic solvents or water.

[0193] 32. The coating composition according to any preceding aspect, wherein the cured coating composition comprises a flexible thermoset resin wherein the flexible thermoset resin demonstrates a flexibility of below 5T determined according to ASTM D D3794-22.

[0194] 33. A method of coating a substrate, wherein the coating composition according to any one of aspects 1 through 32 is applied to a substrate to form a coating layer and cured using actinic radiation and / or ionizing radiation.

[0195] 34. The method according to aspect 33, wherein the ionizing radiation is applied for less than 1 seconds, or from 0.01 to 0.75 seconds or from 0.1 to 0.5 seconds.

[0196] 35. The method according to either one of aspects 33 and 34, wherein the ionizing radiation is applied in an amount sufficient to cure the coating composition.

[0197] 36. The method according to any one of aspects 33 through 35, wherein the ionizing radiation is applied in an amount ranging from 0.1 megarads to 20 megarads, or from 1 megarad to 17 megarads, or from 2 megarads to 15 megarads.

[0198] 37. The method according to any one of aspects 33 through 36, wherein actinic radiation is applied in an amount sufficient to cure the coating composition.

[0199] 38. The method according to any one of aspects 33 through 37, wherein actinic radiation is applied in an amount ranging from 200 mJ / cm2to 3,000 mJ / cm2, or from 250 mJ / cm2to 2,500 mJ / cm2or from 300 mJ / cm2to 2,000 mJ / cm2.

[0200] 39. The method according to any one of aspects 33 through 38, wherein the actinic radiation is applied for less than 2 seconds, or from 0.05 to 1 second or from 0.1 to 0.75 seconds.

[0201] 40. The method according to any one of aspects 33 through 39, wherein the substrate is a metal substrate comprising cold rolled steel, hot rolled steel, electrogalvanized steel, hot dipped galvanized steel, steel plated with zinc alloy, aluminum, aluminum alloys, zinc-aluminum alloys, aluminum plated steel, aluminum alloy plated steel, zinc / magnesium alloy, and / or zinc / magnesium / aluminum alloy,

[0202] 41. The method according to any one of aspects 33 through 40, wherein the cured coating layer has a film thickness of from 0.1 micron to 100 micron, or from 2 micron to 75 micron or from 3 micron to 60 micron determined according to NF EN 13523-1 (2024).

[0203] 42. The method according to any one of aspects 33 through 41, wherein the substrate is treated with a pretreatment composition prior to the coating composition being applied.

[0204] 43. The method according to any one of aspects 33 through 42, wherein the surface of the substrate is cleaned prior to any treating or application of the coating composition.

[0205] 44. The method according to any one of aspects 33 through 43, wherein a primer coating is applied to the substrate prior to application of the coating composition.

[0206] 45. The method according to any one of aspects 33 through 44, wherein one or more basecoats are applied to the substrate after application of a primer coating and prior to application of the coating composition.

[0207] 46. The method according to any one of aspects 33 through 45, wherein a topcoat is applied after application of the coating composition.

[0208] 47. The method according to any one of aspects 33 through 46, wherein the cured coating composition has a T-bend of 2T with no pick-off of paint using an adhesive tape and 4T without any sign of cracking on the coating surface both according to ASTM D4145-10.

[0209] 48. The method according to any one of aspects 33 through 47, wherein the cured coating composition has a tape adhesion rating of 5B determined according to ASTM 3359-23.

[0210] 49. The method according to any one of aspects 33 through 48, wherein the cured coating composition has a gloss retention rating of at least 80 % after 2,000 hours QUVA determined according to ASTM 4587 (2019).

[0211] 50. The method according to any one of aspects 33 through 49, wherein the cured coating composition on the substrate demonstrates minimal chalk formation obtaining a score of at least 7 when determined according to ASTM D4214-07.

[0212] 51. The method according to any one of aspects 33 through 50, wherein the cured coating composition on the substrate demonstrates minimal fade as indicated by a loss of color calculated in Hunter AE units in accordance with ASTM D2244-11 of less than 5 AE Hunter units.

[0213] 52. The method according to any one of aspects 33 through 51, wherein the cured coating composition on the metal substrate demonstrates solvent resistance as demonstrated by greater than 100 double rubs as determined according to NF EN 13523-11 (2019).

[0214] 53. The cured coating composition according to this disclosure on the metal substrate that demonstrates scratch resistance as demonstrated by greater than 2200 g determined according to NF EN 13523-12 (2007).

[0215] 54. A coated substrate prepared according to any one of the methods of aspects 33 through 52.

[0216] The disclosure will be further described by reference to the following non-limiting examples.VI. ExamplesExample 1:

[0217] A coating composition was formulated combining the ingredients in Table 1.Table 1: Formulation of Example 1 material1Laromer UA 9136 available from BASF SE2Disperbyk 180 available from BYK3solvent free aluminum flake available from ECKART4S-275 available from Shamrock5Orgasol 2001 EXD natl available from Arkema6Tinuvin 123 available from BASF SE7Tinuvin 400 available from BASF SE8BYK 3762 available from BYK9Omnirad 2022 available from 1GM Resins

[0218] The coating composition of Table 1 was a liquid as demonstrated by having a flow time determined using a DIN 4 cup at 25 °C of 46 seconds. The coating composition was applied to a galvanized steel coil substrate moving at 10 m / min with UV exposure using a Ga UV bulb, 200 W / cm2at 100% power for 0.5-0.6 seconds followed by electron beam exposure of 125 kV at 50 kGy per second. The coating on the galvanized steel substrate had the properties shown in Table 2.Table 2: Properties of Example 1 materialExample 2:

[0219] A coating composition was formulated combining the ingredients in Table 3.Table 3: Formulation of Example 2 material10Ebecryl 8315, available from Allnex11Disperbyk 2155, available from Byk12Byk 307, available from Byk13cyclic trimethylopropane formal acrylate CTFA-SR531 available from Arkema14Tiona 880, available from Tronox15Black 30C941, available from Shepherd16Lanco PP1362D, available from Lubrizol17Deuteron MK-F6, available from Deuteron Gmbh182,4,6-trimethylbenzoyl diphenylphosphine oxide (TPO)

[0220] Paint Making: To 'A pint can, 30.9 grams of Ebecryl 8315, a tetrafunctional aliphatic urethane acrylate that contains -20% HPMA (hydroxypropyl methacrylate) reactive diluent as a final product supplied by Allnex. 0.62 g of Disperbyk 2155 dispersant and 0.38 g of Byk 307 an additive, both supplied by Byk were added. To that 2.1 g of HDD A and 10.38 g of CTFA, bothavailable from various suppliers, were added to form the premix. The premix was then stirred for a few minutes under air mixer agitation using an air mixer on medium speed using a cowles blade.

[0221] While the premix was mixing, the TPO photoinitiator (1 g) was predissolved into the rest of the CTFA (24.58 g) reactive diluent / monomer. Agitation or gentle heat <35 °C was used to expedite the dissolving of the photoinitiator. Predissolving the solid photoinitiator into the solution ensures it is fully dissolved prior to use.

[0222] Next the titanium dioxide (Tiona 880) and chromium iron oxide black (Black 30C941) pigments, supplied by Tronox and Shepherd respectively, were added under slow agitation. The mix was then mixed with high-speed agitation for 30 minutes. After 30 minutes, the Hegman (fineness of grind) measurement was taken. If a measurement of less than 6 Hegman was observed, additional time dispersing was applied. After a measurement of 6 Hegman or greater is achieved, the remaining products: Lanco PP1362D wax (from Lubrizol) and Deuteron MK-F6 (from Deuteron GmbH) were added with very slow agitation, to reduce pluming. The mixture was then combined with the TPO / CTFA mixture, prepared separately as described above, and mixed for about 10 min at high speed agitation. Note that some of the CTFA / TPO mixture was used while adding to also help reduce pluming and aid in better mixing.

[0223] Panel Application:

[0224] Paint was drawn down using a #16 wire wound bar for application onto the preprimed panels. This yields a coating of- .65 - .75 mils.

[0225] The panels were then subjected to UV curing using a Miltec UV curing apparatus. This UV prior to electron beam curing is a critical step in achieving gloss adjustment. One skilled in the art of radiation cure understands that other forms of radiation or formulation adjustments (texturing adjects) or physical embossing are available to adjust gloss.

[0226] Two gallium doped mercury bulbs of 650 wattage were used for the precuring of the UV coating. The Miltec parameters were set to a line speed of 100 ft / m, 100% intensity for both bulbs and height of 0 in. The device had a - 3 in gap space between the lamp and the belt, so that the substrate can enter and move freely without touching the lamp. The height of the lamps could then be adjusted further using the height adjustment of the Miltec.

[0227] The panels were placed onto the belt and through the Miltec the panels received a dosage of UV radiation.

[0228] With these settings above the UV dosage was as follows, with wavelengths reflecting values commonly accepted in the art:Table 4: UV curing parameters

[0229] The dosages here were taken with an EIT 2.0 Power Puck® II radiometer, from EIT 2.0 LLC. These are the results of two different measurements of the settings of the Miltec.

[0230] Once the panels exited the Miltec, panels were then able to enter the Electron Curing device. This is a product manufactured by the company SKAN.

[0231] Settings are set to the following parameters on the equipment:

[0232] Line Speed: 12 m / min

[0233] Gap Distance: 25 mm

[0234] Voltage: 125kV

[0235] Dosage: 50 kGy

[0236] Oxygen : < 200 ppm

[0237] After electron beam treatment, the panels were tested.Table 5: Paint PropertiesExample 3:

[0238] Example 3 utilized an aliphatic urethane diacrylate in combination with an aliphatic urethane triacrylate. There are a few other differences between Example 2 and Example 3.

[0239] Besides oligomers, Example 3 utilized a different monomer package of TBCH and TMCHA reactive diluents / monomers and less matting agent. The mixing follows the mixing schedule and curing conditions of Example 2.Table 6: Formulation o f the Example 3 material19CN991, from Sartomer20Genomer 4337, from Rahn AG21Disperbyk 180, from Byk224- / c77-butylcyclohexyl acrylate (“TBCH”)23Tiona 880, available from Tronox24Black 30C941, available from Shepherd23Lanco PP1362D, available from Lubrizol26Deuteron MK-F6, available from Deuteron GmbH273,3,5 trimethyl cyclohexanol acrylate (TMCHA) SR420 available from Sartomer282,4,6-trimethylbenzoyl diphenylphosphine oxide (TPO)Table 7: Properties of the Example 3 material

[0240] The results demonstrate that a coil coating composition used according to this disclosure provides excellent results to the coated substrate.

[0241] Whereas particular embodiments 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 can be made without departing from what is defined in the appended claims.

Claims

CLAIMS:

1. A coating composition, comprising components comprising a urethane (meth)acrylate oligomer, such as a polyester urethane (meth)acrylate oligomer, and a monomeric (meth)acrylate ester; wherein the components are curable when exposed to actinic radiation and / or ionizing radiation; and wherein the composition has a flow time of from 40 to 180 seconds determined using a 4 mm Din Flow Cup determined according to DIN 53211 (1987) at 25 °C.

2. The coating composition according to claim 1 , comprising a urethane (meth)acrylate oligomer other than the urethane (meth)acrylate oligomer.

3. The coating composition according to any preceding claim, wherein the monomeric (meth)acrylate ester comprises a difunctional monomer.

4. The coating composition according to any preceding claim, wherein the coating composition comprises less than 3 wt.% of volatile organic compounds.

5. The coating composition according to any preceding claim comprising a photoinitiator.

6. The coating composition according to any preceding claim comprising an organic matting agent.

7. The coating composition according to any preceding claim, wherein the coating composition is essentially free (less than 1 wt.%), substantially free (less than 0. 1 wt.%) or completely free (undetectable by FTIR) of inorganic matting agents.

8. The coating composition according to any one of claims 1 through 6 comprising an inorganic matting agent.

9. The coating composition according to any preceding claim comprising a colorant comprising a pigment and / or a dye.

10. The coating composition according to any preceding claim comprising:A. from 15 to 35 wt.% of the urethane (meth)acrylate oligomer;B. from 0 to 5 wt.% or from 0.1 to 5 wt.% of a urethane (meth)acrylate oligomer other than the polyester urethane (meth)acrylate oligomer;C. from 30 to 75 wt.% of a monofunctional monomeric (meth)acrylate ester;D. from 0 to 10 w.% or from 1 to 10 wt.% of a difunctional monomer;E. from 0 to 5 wt.%, or from 0 to 3 wt.% or from 0.3 to 3 wt.% of a photoinitiator, based on the weight of the coating composition;F. from 0 to 10 wt.% or from 1 to 10 wt.% of an organic matting agent; andG. from 0 to 50 wt.% or from 1 to 50 wt.% of a coloring agent.

11. The coating composition according to any preceding claim, wherein the ionizing radiation is applied in an amount sufficient to cure the coating composition.

12. A method of coating a substrate, wherein the coating composition according to any one of claims 1 through 11 is applied to a substrate to form a coating layer and cured using actinic radiation and / or ionizing radiation.

13. The method according to claim 12, wherein the ionizing radiation is applied for less than 1 seconds, or from 0.01 to 0.75 seconds or from 0.1 to 0.5 seconds, and / or wherein the actinic radiation is applied for less than 2 seconds, or from 0.05 to 1 second or from 0.1 to 0.75 seconds.

14. The method according to either one of claims 12 and 13, wherein the ionizing radiation is applied in an amount sufficient to cure the coating composition.

15. The method according to any one of claims 12 through 14, wherein the ionizing radiation is applied in an amount ranging from 0. 1 megarads to 20 megarads, or from 1 megarad to 17 megarads, or from 2 megarads to 15 megarads.

16. The method according to any one of claims 12 through 15, wherein actinic radiation is applied in an amount sufficient to cure the coating composition.

17. The method according to any one of claims 12 through 16, wherein actinic radiation is applied in an amount ranging from 200 mJ / cm2to 3,000 mJ / cm2, or from 250 mJ / cm2to 2,500 mJ / cm2or from 300 mJ / cm2to 2,000 mJ / cm2.

18. The method according to any one of claims 12 through 17, wherein the substrate is a metal substrate comprising cold rolled steel, hot rolled steel, electrogalvanized steel, hot dipped galvanized steel, steel plated with zinc alloy, aluminum, aluminum alloys, zinc-aluminum alloys, aluminum plated steel, aluminum alloy plated steel, zinc / magnesium alloy, and / or zinc / magnesium / aluminum alloy; and / or wherein the cured coating layer has a film thickness of from 0.1 micron to 100 micron, or from 2 micron to 75 micron or from 3 micron to 60 micron.

19. The method according to any one of claims 12 through 18, wherein the cured coating composition has a T-bend of 2T with no pick-off of paint using an adhesive tape and 4T without any sign of cracking on the coating surface both according to ASTM D4145-10; and / or wherein the cured coating composition has a tape adhesion rating of 5B determined according to ASTM 3359-23; and / or wherein the cured coating composition has a gloss retention rating of at least 80 % after 2,000 hours QUVA determined according to ASTM 4587 (2019); and / or wherein the cured coating composition on the substrate demonstrates minimal chalk formation obtaining a score of at least 7 when determined according to ASTM D4214- 07; and / or wherein the cured coating composition on the substrate demonstrates minimal fade as indicated by a loss of color calculated in Hunter AE units in accordance with ASTM D2244-11 of less than 5 AE Hunter units.

20. A coated substrate prepared according to any of the methods of claims 12 through 19.

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