Methods of curing acetoacetate-containing coating compositions

Abstract

Disclosed are methods of curing a composition comprising (a) an acetoacetate-containing compound and (b) a blocked polyamine. The method includes exposing the composition to electromagnetic radiation generated by a laser to cure the composition. Also disclosed are substrates comprising a coating cured by any of the methods disclosed herein.

Description

METHODS OF CURING ACETOACETATE-CONTAINING COATING COMPOSITIONSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of U.S. Provisional Patent Application Serial No. 63 / 688,125, filed August 28, 2024, entitled “Liquid Coating Compositions Containing Photothermally Active Materials, Coated Substrates, and Methods of Coating Substrates,” and U.S. Provisional Patent Application Serial No. 63 / 714,497, filed October 31, 2024, entitled “Coating Compositions Containing Photothermally Active Materials, Coated Substrates, and Methods of Coating Substrates”, each of which is incorporated herein by reference in its entirety.FIELD

[0002] Methods of curing a composition containing an acetoacetate-containing compound using electromagnetic radiation are disclosed.BACKGROUND

[0003] Multiple industries, including industrial, aerospace, and automotive industries, have demonstrated a desire for cure-on-demand products.SUMMARY

[0004] Disclosed are methods of curing a composition, comprising exposing the composition to electromagnetic radiation generated by a defocused laser to cure the composition; wherein the composition comprises (a) an acetoacetate-containing compound and (b) a blocked polyamine.

[0005] Also disclosed are substrates comprising a coating formed from a composition cured by the disclosed methods.DETAILED DESCRIPTION

[0006] Disclosed herein are methods of curing a composition comprising exposing the composition to electromagnetic radiation generated by a laser and / or an LED to cure the composition.

[0007] As described in more detail below, the composition may comprise (a) an acetoacetate-containing compound and (b) a blocked polyamine.Electromagnetic Radiation and Laser

[0008] Exposure of any of the compositions disclosed herein to electromagnetic radiation (“EMR”) may cure the compositions disclosed herein. As used herein, “electromagnetic radiation” refers to a form of energy that includes visible light and near’ infrared (“nIR”) light. The EMR may be generated by a laser and / or a light emitting diode (“LED”). As used herein, “visible light” refers to EMR with wavelengths in the range of 380 nm to 750 nm which is visible to the human eye. As used herein, “near infrared light” refers to EMR with wavelengths in the range of greater than 750 nm to 2,500 nm.

[0009] The EMR may have a wavelength of at least 300 nm, such as at least 350 nm, such as at least 380 nm, such as at least 400 nm, such as at least 450 nm, such as at least 500 nm, such as at least 550 nm, such as at least 600 nm, such as at least 700 nm, such as at least 800 nm, such as at least 900 nm, such as at least 925 nm, such as at least 950 nm, such as at least 960 nm.

[0010] The EMR may have a wavelength of no more than 1 ,500 nm, such as no more than 1,250 nm, such as no more than 1,080 nm, such as no more than 1,000 nm, such as no more than 985 nm, such as no more than 980 nm, such as no more than 810 nm, such as no more than 530 nm, such as no more than 450 nm.

[0011] The EMR may have a wavelength of 300 nm to 1,500 nm, such as 300 nm to 1,000 nm, such as 300 nm to 980 nm, such as 300 nm to 810 nm, such as 300 nm to 530 nm, such as 300 nm to 450 nm, such as 380 nm to 1,500 nm, such as 380 nm to 1,000 nm, such as 380 nm to 980 nm, such as 380 nm to 810 nm, such as 380 nm to 530 nm, such as 380 nm to 450 nm, such as 400 nm to 1,500 nm, such as 400 nm to 1,250 nm, such as 400 nm to 1,000 nm, such as 400 nm to 980 nm, such as 450 nm to 1,500 nm, such as 450 nm to 1,250 nm, such as 450 nm to 1,000 nm, such as 450 nm to 980 nm, such as 500 nm to 1,500 nm, such as 500 nm to 1,250 nm, such as 500 nm to 1,000 nm, such as 500 nm to 980 nm, such as 550 nm to 1,500 nm, such as 550 nm to 1,250 nm, such as 550 nm to 1,000 nm, such as 550 nm to 980 nm, such as 600 nm to 1,500 nm, such as 600 nm to 1,250 nm, such as 600 nm to 1,000 nm, such as 600 nm to 980 nm, such as 700 nm to 1,500 nm, such as 700 nm to 1,250 nm, such as 7000 nm to 1,000 nm, such as 700 nm to 980 nm, such as 800 nm to 1,500 nm, such as 800 nm to 1,250 nm, such as 800 nm to 1,000 nm, such as 800 nm to 980 nm, such as 900 nm to 1,500 nm, such as 900 nm to 1,250 nm, such as 900 nm to 1,080 nm, such as 900 nm to 1,000 nm, such as 900 nm to 980 nm, such as 925 nm to 1,500 nm, such as 925 nm to 1,250 nm, such as 925 nm to 1,000 nm, such as925 nm to 980 nm, such as 950 nm to 1 ,500 nm, such as 950 nm to 1 ,250 nm, such as 950 nm to 1,000 nm, such as 950 nm to 980 nm, such as 960 nm to 985 nm.

[0012] The EMR may be generated as a continuous wave, a quasi-continuous wave, and / or a pulsed wave. As used herein, “continuous wave,” when used with respect to EMR, refers to a constant, uninterrupted beam of light as long as the laser is powered and having a duty cycle of 100%. As used herein, “quasi-continuous wave,” when used with respect to EMR, refers to a series of pulses of light beams with intervals of no emission and having a duty cycle of greater than 50% to less than 100%. As used herein, “pulsed wave,” when used with respect to EMR, refers to a series of pulses of light beams with a duration of femtoseconds to milliseconds separated by intervals of no emission and having a duty cycle of greater than 0% to 50%. As used herein, “duty cycle” refers to the percentage of time that light is actively emitted by laser during a given period of operation. Duty cycle may be calculated according to the following formula: Duty Cycle (D) = (Pulse Duration) / (Pulse Period) * 100%, where “pulse duration” is the time interval during which the laser emits light in one pulse, wherein “pulse period” is the total time interval of one cycle including the pulse duration plus the off time (when the laser is not emitting light). The person skilled in the art of laser technologies will understand that the selection of duty cycle impacts thermal management and power output and must be compatible with the cure chemistry and the substrate to which the composition is applied.

[0013] The EMR may be directional. As used herein, the term “directional,” when used with respect to the EMR, refers to light that is emitted in a single direction.

[0014] The EMR may be monochromatic light from the visible domain to the nearinfrared domain. As used herein, the term “monochromatic” refers to light having a narrow bandwidth (+ / - 25 nm) at a nominal wavelength or frequency.

[0015] The EMR may be polychromatic light from the visible domain to the nearinfrared domain. As used herein, the term “polychromatic” refers to a light having primarily two or more wavelengths or frequencies.

[0016] The EMR may be coherent. As used herein, the term “coherent,” when used with respect to the EMR, means that the photons of the light wave oscillate at the same frequency and whose wavelengths are in the same phase.

[0017] The laser may be defocused. As used herein, “defocused,” when used with respect to a laser, refers to a manipulation by optics of a light beam generated by the laser toresult in a divergent light beam of a predetermined shape (i.e., a non-Gaussian and / or wide-area light beam), such as a light beam having a substantially rectangular shape, a substantially square shape, and the like.

[0018] The laser may generate EMR that is diffuse, divergent, and / or collimated. As used herein, “diffuse,” when used with respect to EMR, refers to light that is scattered by molecules, particles, or surfaces before reaching its destination. As used herein, “divergent,” when used with respect to EMR, refers to a light beam that spreads out or expands as it propagates away from the light source. The diameter of a divergent EMR light beam increases with distance from the source. As used herein, “collimated,” when used with respect to EMR, refers to a plurality of light rays that are parallel or substantially parallel, resulting in a beam that does not diverge or converge over a specified distance, i.e., the beam maintains a substantially constant diameter and direction over a specified distance.

[0019] Suitable examples of a laser include a solid-state laser, a gas laser, a semiconductor (diode) laser, a fiber laser, a dye laser, and / or a high harmonic generation laser (such as a frequency-doubled or a frequency-tripled laser).

[0020] Suitable examples of a solid-state laser include a neodymium-doped yttrium aluminum garnet (ND:YAG) laser, a ruby laser, a titanium-doped sapphire (Ti:Sapphire) laser, a neodymium-doped yttrium orthovanadate (Nd:YVO4) laser, and / or an erbium-doped yttrium aluminum garnet (Er:YAG) laser.

[0021] Suitable examples of a gas laser include a helium-neon (He-Ne) laser, a carbon dioxide (CO2) laser, an argon ion laser, a nitrogen laser, and / or an excimer laser such as KrF, ArF, and the like.

[0022] Suitable examples of a semiconductor (diode) laser include an edge-emitting laser diode, a vertical-cavity surface-emitting laser (VCSEL), a quantum cascade laser, a distributed feedback (DFB) laser, and / or a distributed bragg reflector (DBR) laser. Suitable materials used to produce NIR diode lasers include gallium arsenide (GaAs), indium gallium arsenide phosphide (InGaAsP) on an indium phosphide (InP) substrate, and / or indium gallium arsenide (InGaAs) on GaAs or InP.

[0023] Suitable examples of a fiber laser include an ytterbium-doped fiber laser, an erbium-doped fiber laser, a thulium-doped fiber laser, a holmium-doped fiber laser, and / or a Raman fiber laser.

[0024] Suitable examples of a dye laser include a rhodamine 6G dye laser, a coumarin dye laser, a stilbene dye laser, a pyrromethene dye laser, and / or a DCM dye laser.

[0025] Any suitable laser diode configuration may be used. For example, the laser diode configuration may comprise a single diode, a diode laser bar, and / or a diode laser stack. As used herein, a “single diode” laser refers to a single semiconductor device in which a diode pumped with electrical current creates lasing conditions at the diode’s junction. Single diodes may be electrically connected such that the decline or failure of any one diode does not affect the output of the still-operational diodes. As used herein, a “diode laser bar” refers to an array of single diodes positioned side-by-side on a single semiconductor chip. A diode laser bar may comprise, for example, 10 to 50 emitters spaced apart, such as 100 pm to 200 pm apart, and connected in parallel or in series. As used herein, a “diode laser stack” refers to an assembly of multiple diode laser bars stacked vertically or arranged in arrays. A diode laser stack may comprise, for example, 5 or more diode laser bars, such as up to 20 diodes, such as up to 300 diodes, such as more than 300 diodes.

[0026] The diode laser stack may be coupled, such as pigtail-coupled, to more than one fiber or may be configured as a bundle of fibers. As used herein, “pigtail -coupled” refers to a laser diode that is permanently connected to an optical fiber, forming a single unit. Fibers may comprise multi-mode fibers with core diameters of, for example, 100 pm to 600 pm or larger.

[0027] The laser may have a wall plug efficiency of at least 30 percent, such as at least 50 percent, such as at least 60 percent, such as at least 80 percent, such as 30 percent to 80 percent, such as 50 percent to 80 percent, such as 60 percent to 80 percent, such as 30 percent to 50 percent. As used herein, “wall plug efficiency” refers to a ratio of usable output power to the total electrical power consumed from the wall outlet; it measures how effectively electrical power from a wall outlet is converted into usable power.

[0028] Adaptive optics may be used to enhance the capabilities of the laser and / or LED, such as those useful for tailoring focal intensity and wide-area distribution of the EMR.

[0029] A laser and / or an LED may be used to cure coatings over a variety of types of substrate surfaces having a range of surface areas, including a vehicle, such as an automobile, a tractor, a trailer, or an aerospace vehicle, an aerospace structure such as a wing, a skin, and / or a fuselage of an aerospace vehicle, a body in white (that is, the stage before painting in automobile manufacturing in which a car body's frame has been joined together), an appliance or a partthereof, a roof, a door, a ship, a large and / or fixed object or structure such as a bridge, a building, an off-shore platform and the like, and pails of any of the foregoing. As used herein, “fixed” when used with respect to an object or a structure refers to an object or a structure that is designed to remain stationary. The laser optionally may include a fiber amplifier to boost the power generated by the laser.

[0030] The laser and / or LED may be coupled with a temperature sensor and / or an IR sensor to control coating temperature, ramp rate, substrate temperature, and the like. Suitable sensors include a pyrometer, an infrared camera, a thermocouple, and other types of sensors that send information to control feedback loops known to those skilled in the art to control coating temperature, ramp rate, substrate temperature, and the like.

[0031] EMR may be generated by an industrial-sized laser or LED equipment, such as equipment configured for use in a laboratory or on a production line. Accordingly, the methods disclosed herein may be used in a laboratory or industrial settings.

[0032] EMR may be generated by a portable laser and / or LED, a hand-held laser and / or LED, a fixed laser and / or LED. Accordingly, the methods disclosed herein may be used in the field, on an existing structure or vehicle, on a fixed structure, and / or as part of a production line for coating substrates.

[0033] EMR may be generated by a robotically guided laser and / or LED.Photothermally Active Material

[0034] Optionally, the composition may comprise a photothermally active material. As used herein, a “photothermally active material” refers to a material whose presence in a composition reduces by at least 5% the total energy density required to ramp and maintain the composition at a temperature setpoint compared to the total energy density required to ramp and maintain the same composition that does not include the material at the temperature setpoint. As used herein, “total energy density” is calculated according to Equation 1:Equation 1, where Etot = total energy density in J / cm2; to = time zero or start of heating cycle;= time to end of heating cycle, wherein the time from to to tmax includes ramp time to a temperature setpoint and hold time at the temperature setpoint (in seconds); %P = the percentageof laser power used in the recorded time interval (as recorded using LASCON Process Manager software by Dr. Mcrgcnthalcr GmbH & Co. KG, as part of the controller of the laser system; Lp = laser power, 4500 W; At = 0.02 seconds between recorded data points, ; and A = the projection area of the laser output, 400 cm2. As used herein, “temperature setpoint” refers to a preset temperature to which the coating is ramped and at which the coating is maintained over the heating cycle. Temperature setpoint may be measured using an infrared thermometer or similar device to measure the temperature of the coating. Temperatures from the infrared thermometer may be read by the controller described above to adjust the EMR generated by the laser system over the heating cycle to ramp or maintain the coating temperature at the temperature setpoint.

[0035] The photothermally active material may be a solid, a neat liquid, a solid dissolved in an aqueous or organic solvent, a dry powder, a solid dispersed in an aqueous or organic solvent, or dispersed in an organic medium that is non-volatile such as a plasticizer or a reactive diluent.

[0036] The photothermally active material that may be used in the compositions disclosed herein include boron nitride; silicon nitride; silicon dioxide; silicon carbide; aluminum nitride; boron arsenide; aluminum oxide; magnesium oxide; dead burned magnesium oxide; beryllium oxide; titanium oxide; zinc oxide; nickel oxide; copper oxide; tin oxide; aluminum oxide; aluminum trihydrate; manganese dioxide; magnesium hydroxide; agate; emery; ceramic microspheres; metakaolin; and / or diamond.

[0037] The photothermally active material that may be used in the compositions disclosed herein also include diatomaceous earth; clay, such as kaolin, bentonite, and halloysite; talc; mica; leucophyllite; lazurite; and / or silica, such as precipitated silica, pyrogenic silica and silica gel, sulfur containing sodium silicates, cristobalite, wollastonite, feldspar, leucophyllite, chamotte, perlite, glass powder and flake, quartz, metal and mixed metal silicate, such as aluminum silicate, barium silicate, barium copper silicate, calcium copper silicate, and sulfur containing sodium silicate, and / or other inorganic silicate and derivates such as orthosilicate, such as lithium orthosilicate and / or inorganic phosphosilicate.

[0038] The photothermally active material that may be used in the compositions disclosed herein also include lime; iron oxide such as hematite, magnetite and siderite; chromium oxide; hydrated chromium oxide; chromium trioxide; antimony trioxide; antimony pentoxide;antimony tin oxide; indium tin oxide; cerium oxide; titanium dioxide, such as rutile and anatase titanium dioxide; tungsten oxide; doped tungsten oxides having the formula MxWCh such as CsWCh; reduced tungsten oxide such as violet tungsten oxide; tungstate; tungsten bronzes; vanadium oxide; cupric carbonate hydroxide; copper hydroxide; layered double hydroxide such as hydrotalcite; titanium nitride; and / or organic quaterrylene.

[0039] The photothermally active material that may be used in the compositions disclosed herein also include calcium carbonate; dolomite; huntite; and / or hydromagnesite.

[0040] The photothermally active material that may be used in the compositions disclosed herein also include zinc chromate; zinc tetraoxy chromate; barium chromate; lead chromate; strontium chromate; and / or other inorganic chromates.

[0041] The photothermally active material that may be used in the compositions disclosed herein also include barium sulfate and / or barium manganate sulfate.

[0042] The photothermally active material that may be used in the compositions disclosed herein also include carbon black; graphite; graphene; and / or graphenic carbon particles. Graphene may be a thermal graphene such as turbostatic thermal graphene. Graphene may be in the form of commercially available nanoparticles such as exfoliated graphite. Graphenic carbon particles (i) may be thermally produced from a hydrocarbon precursor material capable of forming a two-carbon-fragment species or a hydrocarbon material comprising methane introduced into a thermal zone at a temperature of greater than 3,500°C, (ii) may have an average aspect ratio of greater than 3:1, (iii) may have a BET specific surface area of greater than 70 m2 / g, and / or (iv) may have a Raman spectroscopy 2D / G peak ratio of at least 0.9:1. Graphenic carbon particles may be produced by methods such as those disclosed in U.S. Patent No. 8,486,363 and U.S. Patent No. 8,486,364, each incorporated herein by reference in its entirety.

[0043] As used herein, the term “graphenic carbon particles” means carbon particles having structures comprising one or more layers of one-atom-thick planar sheets of sp2-bonded carbon atoms that are densely packed in a honeycomb crystal lattice. The average number of stacked layers may be less than 100, for example, less than 50. The average number of stacked layers may be 30 or less, such as 20 or less, 10 or less, or, in some cases, 5 or less. The average number of stacked layers may be greater than 2, for example, greater than 3, or greater than 4. At least a portion of the graphenic carbon particles may be in the form of platelets that aresubstantially curved, curled, creased, or buckled. The graphenic carbon nanoparticles may be turbostatic, i.c., adjacent stacked atom layers do not exhibit ordered AB Bernal stacking associated with conventional exfoliated graphene but rather exhibit disordered or non- AB AB AB stacking. Alternatively, the graphenic carbon particles may be in the form of nanotubes. The particles typically do not have a spheroidal or equiaxed morphology.

[0044] The photothermally active material that may be used in the compositions disclosed herein also includes cadmium sulfide; cadmium selenide; and / or cadmium sulfoselenide.

[0045] The photothermally active material that may be used in the compositions disclosed herein also include cobalt stannate; cobalt phosphate; and / or cobalt aluminate.

[0046] The photothermally active material that may be used in the compositions disclosed herein also include copper pigment such as copper phthalocyanine, copper / zinc pigment; zinc pigment; bronze pigment; gold bronze pigment; ferric hexacyanoferrate; lithopone; and YInMn blue pigment (yttrium, indium, and manganese pigment); metal flake pigment such as zinc flake; metal effect pigment; and / or inorganic effect pigment.

[0047] The photothermally active material that may be used in the compositions disclosed herein also include phosphate such as chrome phosphate, phosphite, and phosphonate, inorganic phosphate, polyphosphate, orthophosphate, and / or pyrophosphate such as manganese ammonium pyrophosphate.

[0048] The photothermally active material may also include a micronized rubber compound.

[0049] The photothermally active material may be a conjugated material, a dye, a solubilized pigment, and / or a pigment dispersion. As used herein, a “conjugated compound” refers to a compound having two double bonds separated by a single bond, for example two carbon-carbon double bonds with a single carbon-carbon bond between them. Suitable examples of conjugated materials include catechol violet and / or xylenol orange. A suitable example of a solubilized pigment includes Astrad-IS PCN Blue. Suitable examples of dyes include cyanine dyes, phthalocyanine dyes, porphyrin dyes, and / or boron dipyrrin dyes.

[0050] The photothermally active material may comprise carbon black.

[0051] Any combination of the foregoing photothermally active materials disclosed herein above also may be used in the compositions disclosed herein. For example, thephotothermally active material may comprise a single photothermal material or may comprise two or more different types of photothcrmal material.

[0052] The photothermally active material may be soluble or may be in a particulate form.

[0053] Optionally, a photothermally active material of any average particle size can be used in the compositions disclosed herein, provided that the photothermally active material generates sufficient heat for curing to take place when the composition is exposed to EMR. For example, the photothermally active material may be micron sized, such as at least 0.5 microns, such as at least 1 micron, such as no more than 50 microns, such as no more than 15 microns, such as 0.5 to 50 microns, such as 1 to 15 microns, with size based on number average particle size. Alternatively, the photothermally active material may be nano sized, such as at least 10 nanometers, such as no more than 499 nanometers, such as no more than 100 nanometers, such as 10 nanometers to 499 nanometers, such as 10 nanometers to 100 nanometers, with size based on number average particle size. It will be appreciated that these particle sizes refer to the particle size of the photothermally active material at the time of incorporation into the composition. Various coating preparation methods may result in the particles agglomerating, which could increase average particle size, or shearing or other action that can reduce average particle size. Thus, the photothermally active material may be present in the form of particles such as microparticles and / or nanoparticles such as nanowires, nanorods, nanoplatelets, nanosheets, nanospheres, powders, flakes, microspheres, high aspect ratio materials, and irregularly shaped particles of appropriate size. Number average particle size may be measured by methods known to those skilled in the art, for example, using a scanning electron microscope (SEM).

[0054] Optionally, the particles of photothermally active materials have a number average primary particle size of no more than 500 nanometers, such as no more than 50 nanometers, or no more than 2 nanometers. Number average particle size may be measured by methods known to those skilled in the art, for example, using SEM. As used herein, the term “primary particle size” refers to the smallest diameter sphere that will completely enclose an individual particle as opposed to an agglomeration of two or more individual particles.

[0055] The compositions may comprise the photothermally active material in an amount of at least 0.001 percent by weight based on total solids weight of the composition, such as atleast 0.01 percent by weight. The compositions may comprise the photothermally active material in an amount of no more than 10 percent by weight based on total solids weight of the composition, such as no more than 7 percent by weight. The composition may comprise the photothermally active material in an amount of 0.001 percent by weight to 10 percent by weight photothermally active material based on total solids weight of the composition, such as 0.01 percent by weight to 7 percent by weight.Acetoacetate-Containing Compound

[0056] The composition disclosed herein may further comprise an acetoacetate- con taining compound. The acetoacetate-containing compound may comprise a small molecule and / or a polymer comprising an acetoacetate functional group.

[0057] The acetoacetate-containing compound may have an acetoacetate functionality of at least 2, such as no more than 10, such as no more than 5. The acetoacetate-containing compound may have an acetoacetate functionality of 2 to 10, such as 2 to 5.

[0058] The acetoacetate-containing compound may comprise an acetoacetate-functional polyester. The acetoacetate-functional polyester may comprise the transesterification reaction product of reactants comprising a polyester polyol and an acetoacetate-containing reactant. The polyester polyol may be prepared by esterification of an organic polycarboxylic acid or anhydride thereof with an organic polyol and / or an epoxide. A description of the preparation of the acetoacetate-functional polyester may be found in U.S. Patent No. 5,288,802, col. 4, 1. 37 - col. 5, 1. 62, the cited portions of which are incorporated herein by reference.

[0059] The acetoacetate-containing compound may comprise a urethane linkage, which is described more fully in WO 2023 / 076835 A2 at pars.

[0027] -

[0077] , the cited portions of which are incorporated herein by reference.

[0060] The acetoacetate-containing compound may have a number average molecular weight (Mn) of at least 216 g / mol as determined by gas permeation chromatography, such as at least 500 g / mol. The acetoacetate-containing compound may have a number average molecular weight (Mn) of no more than 50,000 g / mol as determined by gas permeation chromatography, such as no more than 40,000 g / mol. The acetoacetate-containing compound may have a number average molecular weight (Mn) of 216 g / mol to 50,000 g / mol as determined by gas permeation chromatography, such as 500 g / mol to 40,000 g / mol. The gas permeation chromatography is measured using Waters 2695 separation module with a Waters 4120 differential refractometer(RI detector) and polystyrene standards, tetrahydrofuran (THF) used as the eluent at a flow rate of 1 ml min"1, and two PL Gel Mixed C columns used for separation.

[0061] The composition may comprise the acetoacetate-containing compound in an amount of at least 1% by weight based on total solids weight of the composition, such as at least 3% by weight, such as at least 5% by weight. The composition may comprise the acetoacetate- containing compound in an amount of no more than 95% by weight based on total solids weight of the composition, such as no more than 90% by weight, such as no more than 85% by weight. The composition may comprise the acetoacetate-containing compound in an amount of 1% by weight to 95% by weight based on total solids wight of the composition, such as 3% by weight to 90% by weight, such as 5% by weight to 85% by weight.Blocked Polyamine

[0062] The composition may comprise a blocked polyamine. As used herein, a “blocked polyamine” refers to an amine in which an amine functional group contains a blocking group formed from reacting the amine functional group with a compound, such as a ketone or aldehyde. When referring to an amine functional group, “blocked” means that the amine functional group contains a blocking group, which results in the amine functional group being non-reactive at ambient conditions.

[0063] Suitable blocked polyamines include aliphatic compounds and aromatic compounds. The blocked polyamine may comprise two or more amine functional groups and a blocking group on at least one amine functional group. The amine functional groups may comprise primary amine functional groups and / or secondary amine functional groups.

[0064] The blocked polyamine may comprise blocked ethylenediamine, diethylenetriamine, hexamethylenediamine, 1 ,2-propanediamine, 2-methy 1-1,5- pentamethylenediamine, 2,2,4-trimethyL 1 ,6-hexanediamine, isophoronediamine, diaminocyclohexane, xylylenediamine, and / or l,12-diamino-4,9-dioxadodecane. For example, the blocked polyamine may be a blocked polyketimine and / or a blocked polyaldimine. Additional suitable blocked polyamines include those in U.S. Patent Application Publication No. 2018 / 0162099 Al at paras.

[0066] -

[0068] , the cited portions of which are incorporated herein by reference.

[0065] The composition may comprise the blocked polyamine in an amount of at least1% by weight based on total solids weight, such as at least 3% by weight, such as at least 5% byweight. The composition may comprise the blocked poly mine in an amount of no more than 95% by weight based on total solids weight, such as no more than 90% by weight, such as no more than 85% by weight. The composition may comprise the blocked polyamine in an amount of 1% by weight to 95% by weight based on total solids weight of the composition, such as 3% by weight to 90% by weight, such as 5% by weight to 85% by weight.Epoxy-Containing Compound

[0066] The composition optionally may further comprise an epoxy-containing compound. The epoxy-containing compound may be monofunctional (also referred to herein as a “monoepoxide”), difunctional (also referred to herein as a “diepoxide”), and / or polyfunctional (also referred to herein as a “poly epoxide”). As used herein, the term “monofunctional” means an atom or molecule that is only capable of reacting to form one new bond. As used herein, the term “polyfunctional” means an atom or a molecule that is capable of reacting to form more than one new bond more than one time through the same atom and / or through multiple single reactions of atoms within the molecule. For clarity, polyfunctional includes difunctional.

[0067] The epoxy-containing compound may be a monomer, a small molecule and / or a polymer. As used herein, “small molecule” refers to a molecule that comprises discrete chemical structures, has a molecular weight of less than 400 g / mol, and that is not a polymer (i.e., is not composed of repeating units). The molecular weight of a small molecule may be determined by mass spectrometry. Appropriate mass spectrometry methods for various types of small molecules are available in many references, such as Mass Spectrometry: A Textbook (3rdEdition, 2018, edited by Jurgen Gross). As used herein, “polymer” refers to a molecule having repeating units and includes oligomers, homopolymers, and copolymers.

[0068] Suitable monoepoxides that may be used include monoglycidyl ethers of alcohols and phenols, such as phenyl glycidyl ether, n-butyl glycidyl ether, cresyl glycidyl ether, isopropyl glycidyl ether, glycidyl versatate, for example, CARDURA E available from Shell Chemical Co., and / or glycidyl esters of monocarboxylic acids such as glycidyl neodecanoate, Epodil 741 available from Evonik, Epodil 746 available from Evonik, and ER1SYS ® GE-7 available from CVC Thermoset Specialties.

[0069] Suitable polyepoxides include polyglycidyl ethers of Bisphenol A, such as Epon® 828 and 1001 epoxy resins, and Bisphenol F diepoxides, such as Epon® 862, which are commercially available from Hexion Specialty Chemicals, Inc. Other suitable polyepoxidesinclude polyglycidyl ethers of polyhydric alcohols, polyglycidyl esters of polycarboxylic acids, polycpoxidcs that arc derived from the epoxidation of an olcfinically unsaturated alicyclic compound, polyepoxides that are derived from the epoxidation of an olcfinically unsaturated nonaromatic cyclic compound, polyepoxides containing oxyalkylene groups in the epoxy molecule, and epoxy novolac resins. Still other suitable polyepoxides include epoxidized Bisphenol A novolacs, epoxidized phenolic novolacs, epoxidized cresylic novolac, and triglycidyl p-aminophenol bismaleimide. The epoxy-containing compound may also comprise an epoxy-dimer acid adduct. The epoxy-dimer acid adduct may be formed as the reaction product of reactants comprising a diepoxide compound (such as a polyglycidyl ether of Bisphenol A) and a dimer acid (such as a C36 dimer acid). The epoxy-containing compound may also comprise a carboxy 1-terminated butadiene-acrylonitrile copolymer modified epoxy- containing compound. The epoxy-containing compound may also comprise epoxidized castor oil. The epoxy-containing compound may also comprise an epoxy-containing acrylic, such as glycidyl methacrylate. The epoxy-containing compound may also comprise an epoxy-containing polymer such as epoxy-containing polyacrylate.

[0070] The epoxy-containing compound may comprise an epoxy-adduct. The composition may comprise one or more epoxy-adducts. As used herein, the term “epoxy- adduct” refers to a reaction product of reactants comprising (i) a first compound that is at least difunctional and comprises at least one epoxide functional group and (ii) a second compound that does not include an epoxide functional group. For example, the epoxy-adduct may comprise the reaction product of reactants comprising: (1) an epoxy compound, a polyol, and an anhydride;(2) an epoxy compound, a polyol, and a diacid; or (3) an epoxy compound, a polyol, an anhydride, and a diacid.

[0071] The epoxy compound used to form the epoxy-adduct may comprise any of the epoxy-containing compounds listed above that may be included in the coating composition.

[0072] The polyol used to form the epoxy-adduct may include diols, triols, tetraols and higher functional polyols, i.e. compounds comprising five or more hydroxyl groups per molecule. Combinations of such polyols may also be used. The polyols may be based on a polyether chain derived from ethylene glycol, propylene glycol, butylene glycol, hexylene glycol and the like as well as mixtures thereof. The polyol may also be based on a polyester chain derived from ring opening polymerization of caprolactone (referred to as polycaprolactone-basedpolyols hereinafter). Suitable polyols may also include polyether polyols, polyurethane polyols, polyurca polyols, acrylic polyols, polyester polyols, polybutadicnc polyols, hydrogenated polybutadiene polyols, polycarbonate polyols, polysiloxane polyols, and combinations thereof. Polyamines corresponding to polyols may also be used, and in this case, amides instead of carboxylic esters will be formed with the diacids and anhydrides.

[0073] The polyol may comprise a polycaprolactone-based polyol. The polycaprolactone-based polyols may comprise diols, triols or tetraols terminated with primary hydroxyl groups. Commercially available polycaprolactone-based polyols include those sold under the trade name Capa™ from Perstorp Group, such as, for example, Capa 2054, Capa 2077A, Capa 2085, Capa 2205, Capa 3031, Capa 3050, Capa 3091 and Capa 4101.

[0074] The polyol may comprise a poly tetrahydrofuran-based polyol. The polytetrahydrofuran-based polyols may comprise diols, triols or tetraols terminated with primary hydroxyl groups. Commercially available poly tetrahydrofuran-based polyols include those sold under the trade name Terathane®, such as Terathane® PTMEG 250 and Terathane® PTMEG 650 which are blends of linear diols in which the hydroxyl groups are separated by repeating tetramethylene ether groups, available from Invista. In addition, polyols based on dimer diols sold under the trade names Pripol®, Solvermol™ and Empol®, available from Cognis Corporation, or bio-based polyols, such as the tetrafunctional polyol Agrol 4.0, available from BioBased Technologies, may also be utilized.

[0075] The anhydride that may be used to form the epoxy-adduct may comprise any suitable acid anhydride known in the ait. For example, the anhydride may comprise hexahydrophthalic anhydride and its derivatives (e.g., methyl hexahydrophthalic anhydride); phthalic anhydride and its derivatives (e.g., methyl phthalic anhydride); maleic anhydride; succinic anhydride; trimellitic anhydride; pyromelletic dianhydride (PMDA); 3,3 ',4,4'- oxydiphthalic dianhydride (ODPA); 3,3',4,4'-benzopherone tetracarboxylic dianhydride (BTDA); and 4,4 '-diphthalic (hexafluoroisopropylidene) anhydride (6FDA).

[0076] The diacid used to form the epoxy-adduct may comprise any suitable diacid known in the art. For example, the diacids may comprise phthalic acid and its derivates (e.g., methyl phthalic acid), hexahydrophthalic acid and its derivatives (e.g., methyl hexahydrophthalic acid), maleic acid, succinic acid, adipic acid, and the like.

[0077] The epoxy-adduct may comprise a diol, a monoanhydride or a diacid, and a diepoxy compound, wherein the mole ratio of diol, monoanhydride (or diacid), and diepoxy compounds in the epoxy-adduct may vary from 0.5:0.8:1.0 to 0.5:1.0:6.0.

[0078] The epoxy-adduct may comprise a triol, a monoanhydride or a diacid, and a diepoxy compound, wherein the mole ratio of triol, monoanhydride (or diacid), and diepoxy compounds in the epoxy-adduct may vary from 0.5:0.8:1.0 to 0.5:1.0:6.0.

[0079] The epoxy-adduct may comprise a tetraol, a mono anhydride or a diacid, and a diepoxy compound, wherein the mole ratio of tetraol, monoanhydride (or diacid), and diepoxy compounds in the epoxy-adduct may vary from 0.5:0.8:1.0 to 0.5:1.0:6.0.

[0080] The epoxy-containing compound may have at least one functional group in addition to the epoxide functional group(s).

[0081] The epoxy-containing compound may have an epoxy equivalent weight of at least 90 g / eq, such as at least 140 g / eq, such as at least 188 g / eq, and may have an epoxy equivalent weight of no more than 2,000 g / eq, such as no more than 1,000 g / eq, such as no more than 500 g / eq. The epoxy-containing compound may have an epoxy equivalent weight of 90 g / eq to 2,000 g / eq, such as 140 g / eq to 1,000 g / eq, such as 188 g / eq to 500 g / eq. As used herein, “epoxy equivalent weight” is determined by dividing the measured Mw of an epoxy-containing compound by the average number of epoxide functional groups present in the epoxy-containing compound. As used herein, “Mw” refers to the weight average molecular weight measured by gel permeation chromatography using a separation module and polystyrene standards and tetrahydrofuran (THF) as the eluent.(Meth) aery late-Containing Compound

[0082] The composition disclosed herein may comprise a (meth)acry late-containing compound. As used herein, a “(meth) aery late-containing compound” refers to a compound comprising an acrylate functional group and / or a methacrylate functional group.

[0083] The (meth)acrylate-containing compound may comprise at least 2 olefinic double bonds, such as 2 to 20 olefinic double bonds.

[0084] The (meth)acrylate-containing compound can include a di(meth)acrylate, a tri(meth)acrylate, and / or a tetra(meth)acrylate. The (meth)acrylate-containing compound may comprise a (meth)acrylic-functional copolymer, an epoxy resin ( mcth)acry late, a polyester(meth)acrylate, a polyether (meth)acrylate, a polyurethane (meth)acrylate, an amino (mcth)acrylatc, a silicone (mcth)acrylatc, and / or a melamine (meth) acrylate.

[0085] Suitable di(meth)acrylates include, for example, ethylene glycol, di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1 ,4-butanediol di(meth)acrylate, 2,3- dimethylpropane l,3-di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetraethylene glycol di(meth) acrylate, tetrapropylene glycol di(meth)acrylate, ethoxylated hexanediol di(meth)acrylate, propoxylated hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, alkoxylated neopentyl glycol di(meth)acrylate, hexylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polybutadiene di(meth)acrylate, thiodiethyleneglycol di(meth)acrylate, trimethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, alkoxylated hexanediol di(meth)acrylate, alkoxylated neopentyl glycol di(meth)acrylate, pentanediol di(meth)acrylate, cyclohexane dimethanol di(meth)acrylate, and / or ethoxylated bis-phenol A di(meth)acrylate.

[0086] Examples of tri and higher (meth)acrylates include glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, trimethylolpropane tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate, and / or dipcntacrythritol penta(meth)acrylate. Other suitable poly(meth)acrylate oligomers include (meth)acrylate of epoxidized soya oil and urethane acrylates of polyisocyanates and hydroxyalkyl (meth)acrylates.

[0087] Suitable polyurethane (meth)acrylates include reaction products of reactants comprising a polyisocyanate and a hydroxyalkyl (meth)acrylate. Suitable polyisocyanates include 1,6-hexamethylene diisocyanate and / or isophorone diisocyanate. Suitable hydroxyalkyl (meth)acrylates include hydroxyethyl (meth)acrylate and / or hydroxypropyl (meth)acrylate. The polyisocyanate and the hydroxy alkyl (meth)acrylate may be reacted in a molar ratio of NCO:OH of 0.5:2.0, such as 0.7: 1.5. Alternatively, the polyisocyanate and the hydroxyalkyl (meth)acrylate may be reacted in a molar ratio of NCO:OH of 3:1, such as 2:1, such as greater than 1:1, to form an NCO-functional reaction product that may be chain extended with a polyol, such as a diol and / or a triol.

[0088] Suitable polyester (meth)acrylates include reaction products of reactants comprising (a) (meth)acrylic acid and / or (meth)acrylic acid anhydride and (b) a polyol. The polyol may comprise a diol, triol, tetraol, or higher polyol. Examples of suitable polyols include glycerol, 1,4-butane diol, 1,6-hexane diol, neopentyl glycol, trimethylol propane, pentaerythritol and / or propoxylated 1,6-hexane diol. The polyester (meth) acrylate may comprise, for example, glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth) acrylate, pentaerythritol tetra(meth)acrylate, and / or dipentaerythritol penta(meth)acrylate.Accelerator

[0089] The composition disclosed herein optionally may comprise an accelerator. As used herein, the term “accelerator” means a substance that increases the rate or decreases the activation energy of a chemical reaction in comparison to the same reaction in the absence of the accelerator. An accelerator may be either a “catalyst,” that is, without itself undergoing any permanent chemical change, or may be reactive, that is, capable of chemical reactions and includes any level of reaction from partial to complete reaction of a reactant.

[0090] The accelerator may be latent, blocked, and / or encapsulated. As used herein, the terms “latent” or “blocked” or “encapsulated”, when used with respect to a nucleophile or an accelerator, means a molecule or a compound that is activated by an external energy source prior to reacting (i.e., crosslinking) or having a catalytic effect, as the case may be. For example, an accelerator may be in the form of a solid at room temperature and have no catalytic effect until it is heated and melts, or the latent accelerator may be reversibly reacted with a second compound that prevents any catalytic effect until the reversible reaction is reversed by the application of heat and the second compound is removed, freeing the accelerator to catalyze reactions.

[0091] The latent accelerator may comprise a reaction product of reactants comprising (i) an epoxy compound, and (ii) an amine and / or an alkaloid. For example, the heat-activated latent accelerator may comprise a reaction product of reactants comprising (i) an epoxy compound and (ii) an amine, or a reaction product of reactants comprising (i) an epoxy compound and (ii) an alkaloid. Such heat-activated latent molecules are described in paras.

[0098] -

[0110] of U.S. Publication No. 2014 / 0150970, the cited portion of which is incorporated herein by reference. Examples of non-limiting commercially available latent accelerators include those molecules comprising a reaction product of reactants comprising (i) an epoxy compound, and (ii) an amine and / or an alkaloid include the products sold under the trade name Ajicure including Ajicure PN-23, Ajicure PN-H, Ajicure PN-31 , Ajicure PN-40, Ajicure PN-50, Ajicure PN-23J, Ajicure PN- 31 J, Ajicure PN-40J, Ajicure MY-24 and Ajicure MY-2, all available from Ajinomoto Fine- Techno Co., Inc.

[0092] Other suitable accelerators that may be used include guanidines, substituted guanidines, substituted ureas, melamine resins, guanamine derivatives, heat-activated cyclic tertiary amines, and / or aromatic amines. Examples of substituted guanidines are methylguanidine, dimethylguanidine, trimethylguanidine, tetramethylguanidine, methylisobiguanidine, dimethylisobiguanidine, tetramethylisobiguanidine, hexamethylisobiguanidine, heptamethylisobiguanidine, and / or cyanoguanidine (dicyandiamide). Representatives of suitable guanamine derivatives which may be mentioned are alkylated benzoguanamine resins, benzoguanamine resins and / or methoxymethylethoxymethylbenzoguanamine. In addition, catalytically active substituted ureas may also be used. Suitable catalytically-active substituted ureas include p-chlorophenyl-N,N- dimethylurea, 4,4’-methylenebis(phenyldimethyl urea), 1,1 -dimethylurea, N-3- (dimethylamino)carbonylaminomethyl-3,5,5-trimethylcyclohexyl-A,iV-dimethylurea, [1,1’ -(4- methyl-m-phenylene)bis(3,3-dimethylurea), 3 -phenyl- 1,1 -dimethylurea (fenuron) or 3,4- dichlorophenyl-N,N-dimethylurea (also known as Diuron).

[0093] Additional examples of suitable accelerators include molecules comprising an unblocked nucleophilic functional group, such as pyridine, imidazole, dimethylaminopyridine, 1- methylimidazole, N,N’ -carbonyldiimidazole, [2,2]bipyridine, 2,4,6-tris(dimethylamino methyl)phenol, and / or 3,5-dimethylpyrazole.

[0094] The accelerator may comprise a tertiary amine, a quaternary amine, and / or a Lewis Acid catalyst. The tertiary amine may comprise a cyclic tertiary amine, such as 1,4- diazabicyclo[2.2.2]octane (“DABCO”), l,8-diazabicylo[5.4.0]undec-7-ene (“DBU”), 1,5- diazabicyclo[4.3.0]non-5-ene (“DBN”), and / or l,5,7-triazabicyclo[4.4.0]dec-5-ene (“TBD”). Examples of suitable quaternary amines include tetrabutylammonium bromide, tetrabutylammonium chloride, and / or benzyltrimethylammonium bromide. Examples of suitable Lewis acid accelerators include bismuth (such as K-Kat 348, commercially available from King Industries), zinc (such as K-Kat XK-635 and XK-672, commercially available from King Industries), and / or tin, such as dibutyltin dilaurate (commercially available from Songwon) and / or dibutyltin diacetylacetonate (commercially available from Kaneka).

[0095] The composition may comprise the accelerator in an amount of at least 0.01% by weight based on total solids weight of the composition, such as at least 0.05% by weight, such as at least 0.1% by weight. The composition may comprise the accelerator in an amount of no more than 10% by weight based on total solids weight of the composition, such as no more than 8% by weight, such as no more than 5% by weight. The composition may comprise the accelerator in an amount of 0.01% by weight to 10% by weight based on total solids weight of the composition, such as 0.05% by weight to 8% by weight, such as 0.1% by weight to 5% by weight.Additives, Fillers, and Solvent

[0096] The composition disclosed herein optionally may comprise an additive. Such additives include a rheology modifier, a reactive diluent, a non-reactive diluent, a dispersant, a tackifier, a thermoplastic polymer, a surface-active agent, a flame retardant, a corrosion inhibitor, a UV stabilizer, a hindered amine light stabilizer (HALS), a colorant, a tint, a plasticizer, an adhesion promoter, an antioxidant, a silane, a silane terminated polymer, a silyl terminated polymer, and / or a moisture scavenger.

[0097] As used herein, the term “reactive diluent” refers to a non-volatile molecule or a compound that is used to lower the viscosity of a resin and / or a composition but that has at least one functional group capable of reacting with a functional group(s) on molecules or compounds in the resin or composition.

[0098] As used herein, the term “non-reactive diluent” refers to a non-volatile molecule or a compound that is used to lower the viscosity of a resin and / or a composition but that does not have a functional group capable of reacting with a functional group(s) on molecules or compounds in the resin or composition.

[0099] As used herein, the term “plasticizer” refers to a molecule or a compound that does not have a functional group capable of reacting with a functional group(s) on molecules or compounds in a composition and that is added to the composition to decrease viscosity, decrease glass transition temperature (Tg), and impart flexibility.

[0100] Additive(s), if present at all, may be present in the composition in a combined amount of at least 0.01% by weight based on total solids weight of the composition, such as at least 0.05% by weight, such as at least 0.1% by weight. Additive(s), if present at all, may be present in the composition in a combined amount of no more than 15% by weight based on totalsolids weight of the composition, such as no more than 10% by weight, such as no more than 5% by weight. Additivc(s), if present at all, may be present in the composition in an amount of 0.01% by weight to 15% by weight based on total solids weight of the composition, such as 0.05% by weight to 10% by weight, such as 0.1% by weight to 5% by weight.

[0101] The composition disclosed herein optionally may comprise a filler. Suitable examples of filler useful in the composition include aluminum hydroxide, mica, wollastonite, calcium carbonate, glass microspheres, clay, or combinations thereof.

[0102] The composition may comprise the filler in an amount of at least 0.1% by weight based on total solids weight of the composition, such as at least 1% by weight. The composition may comprise the filler in an amount of no more than 90% by weight based on total solids weight of the composition, such as no more than 80% by weight. The composition may comprise the filler in an amount of 0.1% by weight to 90% by weight based on total solids weight of the composition, such as 1% by weight to 80% by weight.

[0103] The composition disclosed herein may optionally comprise a solvent. As used herein, the term “solvent” refers to a molecule or a compound that is used to lower the viscosity of the resin, volatilizes under ambient conditions, and does not have a reactive functional group capable of reacting with molecules or compounds in a composition.

[0104] The composition may include a solvent, such as an organic solvent. As used herein, the term “organic solvent” refers to carbon-based substances capable of dissolving or dispersing other substances.

[0105] Suitable organic solvents that can be included in the solvent include, but are not limited to ester, ketone, glycol ether, alcohol, hydrocarbon or mixtures thereof. Suitable ester solvents can include alkyl acetates such as ethyl acetate, n-butyl acetate, n-hexyl acetate, and mixtures thereof. Suitable ketone solvents may include methyl ethyl ketone, methyl isobutyl ketone, and mixtures thereof. Suitable hydrocarbon solvents may include toluene, xylene, aromatic hydrocarbons, and aliphatic hydrocarbons such as hexane, heptanes, and nonane.

[0106] The composition may comprise the solvent in an amount of at least 5% by weight based on total weight of the composition, such as at least 10% by weight, such as at least 20% by weight. The composition may comprise the solvent in an amount of no more than 80% by weight based on total weight of the composition, such as no more than 60% by weight, such as no more than 40% by weight. The composition may comprise the solvent in an amount of 5% byweight to 80% by weight based on total weight of the composition, such as 10% by weight to 60% by weight, such as 20% by weight to 40% by weight, such as 5% by weight to 20% by weight.Compositions

[0107] The composition may be a liquid. As used herein, “liquid” refers to a material having a viscosity of no more than 5,000 Pa-s at 25°C as measured by parallel plate rheology with a plate diameter of 25 mm, a gap of 1.0 mm, and a shear rate of 1 s'1.

[0108] The composition may have a total solids content of at least 20% by weight based on total weight of the composition, such as at least 40% by weight, such as at least 60% by weight, such as at least 80% by weight, and may have a total solids content of 100% by weight based on total weight of the composition. The composition may have a total solids content of 20% by weight to 100% by weight based on total weight of the composition, such as 40% by weight to 100% by weight, such as 60% by weight to 100% by weight, such as 80% by weight to 100% by weight.

[0109] The composition may have an equivalent ratio of (i) acetoacetate functional groups, epoxy functional groups, and (meth)acrylate functional groups to (ii) blocked amine functional groups of at least 0.5:1, such as at least 0.75:1. The composition may have an equivalent ratio of (i) acetoacetate functional groups, epoxy functional groups, and (meth)acrylate functional groups to (ii) blocked amine functional groups of no more than 1.5:1, such as no more than 1.25:1. The composition may have an equivalent ratio of (i) acetoacetate functional groups, epoxy functional groups, and (meth)acrylate functional groups to (ii) blocked amine functional groups of 0.5:1 to 1.5:1, such as 0.75:1 to 1.25:1.

[0110] The composition may be substantially free, essentially free, or completely free of a photopolymerizable initiator.

[0111] The composition may be formulated as a sealant composition, an adhesive composition, a gap filler composition, a pottant composition, a prepreg, and / or a liquid shim composition.

[0112] The composition may be formulated as a one-component composition, a two- component composition, or a higher-component composition.

[0113] As used herein, a “IK” or “one-component” composition is a composition in which all the ingredients may be premixed and stored at ambient conditions and wherein thereactive components do not readily react at ambient or slightly thermal conditions. A one- component composition may cure upon exposure to EMR and / or may react at an accelerated rate upon exposure to EMR compared to a reaction rate in the absence of EMR. In the absence of such exposure, the composition will remain largely uncured.

[0114] As used herein, the term “two-component” or “2K” refers to a composition in which the reactive components readily associate to form an interaction or react to form a bond (physically or chemically), i.e., cure, without activation from an external energy source, such as at ambient or slightly thermal conditions, when mixed. One of skill in the art understands that the two components of the composition are stored separately from each other and mixed just prior to application of the composition. A two-component composition may be exposed to EMR as described herein. As used herein, “reactive components” refer to components of the final composition containing reactive functional groups.

[0115] The compositions disclosed herein may be formulated as a IK composition comprising, consisting essentially of, or consisting of (i) an acetoacetate-containing compound and (ii) a ketimine-containing compound, and (iii) optionally an epoxy-containing compound, a (meth)acrylate-containing compound, a photothermally active material, an accelerator, an additive, a solvent, and / or a filler.

[0116] The compositions disclosed herein may be formulated as a 2K composition comprising, consisting essentially of, or consisting of: a first component comprising, consisting essentially of, or consisting of an acetoacetate-containing compound; and a second component comprising, consisting essentially of, or consisting of a ketimine-containing compound. The first component optionally may further comprise an epoxy-containing compound and / or a (meth)acrylate-containing compound. The first component and / or the second component optionally may further comprise a photothermally active material, an accelerator, an additive, a filler, and / or a solvent. The first and second components may be mixed immediately prior to use.

[0117] The composition may be agitated manually or mechanically to homogenize the ingredients. Volumetric mixers or automated blending devices may be used to homogenize multi-component systems.Methods and Cured Coatings

[0118] Disclosed herein are methods of curing any of the compositions described above.

[0119] The composition may be applied alone or as part of a system that can be deposited in a number of different ways onto a number of different substrates. Accordingly, disclosed herein are methods for treating a substrate comprising, consisting essentially of, or consisting of contacting a surface of the substrate with any of the compositions disclosed herein and exposing the composition to an EMR generated by a laser and / or an LED as described above. The composition can be applied to the surface of the substrate in any number of different ways by depositing, applying, or contacting the composition to the substate surface to form a coating thereon, non-limiting examples of which include extruding, pressing, grouting, caulking, spreading, brushing, rolling, troweling, dipping, spraying, and the like.

[0120] Compositions may be applied in different environments such as a spray booth, a hangar, a production line, a paint shop, an open workspace, or a clean room based on the need to protect the composition from airborne contaminants. Spray booths can be maintained to keep constant temperature and humidity. Enclosures may be used in hangar- operations to help with cleanliness. Ventilation can aid in removing airborne particles, fumes, and overspray while maintaining optimal temperature and humidity conditions. Negative pressure systems or HEPA filters may be used to assist in contaminant removal. Coating repair or application may take place in remote locations lacking booths, hangars, or portable enclosures.

[0121] The method comprises exposing the composition to EMR generated by a laser and / or an LED to cure the composition. Such methods may cure the composition to form a coating. The EMR, laser, and / or LED may be any of those described above. For example, the compositions disclosed herein may be applied to a substrate surface and cured as described herein to form a coating.

[0122] The methods may comprise exposing the composition to EMR for at least 2 minutes.

[0123] The methods may comprise exposing the compositions comprising the acetoacetate-containing compound and the ketimine-containing compound to EMR with a ramp from ambient to a temperature setpoint of at least 100°C and then held at the temperature setpoint of at least 100°C for at least 2 minutes to cure the composition.

[0124] The methods may comprise exposing the compositions to EMR at an intensity of at least 0.01 W / cm2, such as at least 0.1 W / cm2, such as at least 0.2 W / cm2. The methods may comprise exposing the compositions to EMR at an intensity of no more than 108W / cm2, such asno more than 106W / cm2, such as no more than 104W / cm2, such as no more than 102W / cm2, such as no more than 15 W / cm2, such as no more than 12 W / cm2. The methods may comprise exposing the compositions to EMR at an intensity of 0.01 W / cm2to 108W / cm2, such as 0.1 W / cm2to 106W / cm2, such as 0.1 W / cm2to 104W / cm2, such as 0.1 W / cm2to 102W / cm2, such as 0.1 W / cm2to 15 W / cm2, such as 0.2 W / cm2to 12 W / cm2.

[0125] The composition may be cured as described herein to form a coating, such as a sealant, an adhesive, a gap filler, a pottant, a prepreg, and / or a liquid shim.

[0126] The methods disclosed herein may further comprise cleaning and / or deoxidizing the substrate surface prior to applying the composition. Suitable methods of cleaning include solvent- wiping, alkaline cleaning, mechanical cleaning and / or abrasion, ultrasonic cleaning, plasma cleaning or etching, and the like, as understood by those skilled in the art of substrate protection.

[0127] The methods disclosed herein may further comprise coating the substrate surface with a coating composition in addition to the composition disclosed herein. That is, the methods may further comprise treating the substrate surface with a pretreatment composition and / or coating the substrate surface with an electrodepositable coating composition, a primer coating composition, a basecoat coating composition, a topcoat coating composition, an adhesion promoter, and the like, as understood by those skilled in the art of substrate protection. That is, “contacting a surface of the substrate” encompasses contacting a surface of a substrate that has been treated with other coatings, as described herein.

[0128] The methods disclosed herein may comprise applying a composition as described herein to a damaged portion of a substate surface and exposing the composition to EMR generated by a laser and / or an LED as described herein. Optionally, the surface may comprise a pre-existing coating, and the pre-existing coating may be partially removed prior the applying.

[0129] The methods disclosed herein may exclude heating the substrate (i) prior to and / or following applying the composition to a surface of the substrate and / or (ii) prior to and / or following exposing the composition to EMR.

[0130] The method optionally may further comprise contacting a surface of a second substrate to the composition such that the composition is between the first substrate and the second substrate. For example, the composition may be applied to either one or both of the substrate materials such that the composition is positioned between the first and the secondsubstrates. In examples, the substrates may be aligned, and pressure and / or spacers may be added to control bond thickness. Exposure to EMR may be performed prior to or following the addition of the second substrate to form a joint.

[0131] The methods disclosed herein may be performed using a portable and / or handheld laser, as described above. As such, the methods may be performed in the field and / or on existing structures.

[0132] The methods disclosed herein may be performed using an industrial-sized laser or LED equipment, as described above. As such, the methods may be performed in a laboratory and / or industrial setting.

[0133] The methods disclosed herein may be performed using a robotically guided laser and / or LED.

[0134] The methods disclosed herein may maintain the temperature of the composition, for example, without heating the substrate above its heat deflection temperature. As used herein, “heat deflection temperature” refers to the temperature at which a material’s properties are compromised. For example, the substrate may be heated up to 60°C, such as up to 80°C, such as up to 100 C, such as up to 120 C. The temperature of the substrate may not increase following the exposure to EMR, for example, the substrate may not be heated above ambient temperature. Accordingly, the present disclosure allows for reduced energy consumption and may also allow for the use of coatings on temperature sensitive substrates.

[0135] The composition disclosed herein may be applied to a substrate surface and cured as described above to form a coating. Upon exposure of a composition to EMR, the heat generated by the exposure may be localized and sufficient to cure the composition.

[0136] The methods disclosed herein may impart useful dual cure properties to the coating compositions disclosed herein. For example, curing may be initiated by exposure of a composition to EMR and / or following exposure of the composition to EMR. Such dual cure mechanisms may be useful for curing compositions applied to geometries and configurations where it is not possible to directly expose a composition to EMR. For example, a portion of the composition can be exposed to the EMR thereby accelerating cure in the exposed areas, with cure continuing in these areas via a dark cure curing mechanism when the exposure to EMR is stopped. Dark curing mechanisms will also occur in portions of the composition that are not exposed to EMR. As used herein, “dark cure” refers to the ability of thecomponents of a composition to cure in the absence of exposure to EMR. Dark cure may occur over at least 1 day, such as over at least 3 days, such as over at least 4 days, such as over at least 7 days, such as over at least 14 days, such as over at least 21 days, such as over at least 56 days, such over at least 112 days. Surprisingly, while exposure to EMR accelerated cure of the composition, it did not negatively affect the dark curing mechanism.

[0137] It was surprisingly and unexpectedly discovered that exposure of a composition comprising a blocked polyamine-containing compound and an acetoacetate-containing compound as disclosed herein to EMR generated by a laser and / or an LED resulted in sufficient heat generation to initiate cure of the composition. For example, exposure of a composition disclosed herein to EMR generated by a diode laser and having a wavelength of 900 nm to 1 ,080 nm, such as 960 nm to 985 nm, may require a total energy density to ramp and maintain the composition at a temperature of 100°C for at least 2 minutes of less than 500 J / cm2, such as less than 475 J / cm2, such as less than 400 J / cm2, such as less than 300 J / cm2, such as less than 200 J / cm2, such as less than 175 J / cm2.

[0138] It also was surprisingly and unexpectedly discovered that exposure of the composition comprising the blocked polyamine-containing compound and the acetoacetate- containing compound as disclosed herein to EMR generated by a laser and / or an LED accelerated the rate of cure compared to the same composition cured under ambient conditions. For example, exposure of such a composition to EMR generated by a laser and / or an LED and having a wavelength of 900 nm to 1,080 nm, such as 960 nm to 985 nm, may cure the composition following exposure to the EMR for a 30 second ramp from ambient to at least 100°C and held at such temperature for at least 2 minutes. This is demonstrated, for example, by such coatings achieving 100 methyl ethyl ketone (MEK) double rubs (according to ASTM D5402-19) 45 minutes after EMR exposure. By comparison, the same composition cured under ambient conditions did not achieve 100 MEK double rubs 45 minutes after mixing the components, but rather achieved 100 MEK double rubs 24 hours after mixing the components, indicating that exposing a composition comprising acetoacetate to EMR generated by a laser and / or an LED accelerated cure of the composition following exposure to the EMR for a 30 second ramp from ambient to at least 100°C and held at such temperature for at least 2 minutes compared to the same composition cured under ambient conditions. This was a surprising and unexpected result.

[0139] Additionally, it was surprisingly and unexpectedly discovered that coating compositions comprising a blocked polyamine-containing compound, an acetoacetate-containing compound, and a photothermally active material required a reduced total energy density to cure the composition compared to the same composition that did not include the photothermally active material. That is, the compositions disclosed herein comprising a photothermally active material required a reduced total energy density to ramp and maintain the composition at a temperature setpoint (defined in the Examples) compared to the total energy density required to ramp and maintain the same composition that did not include a photothermally active material at the temperature setpoint. For example, the total energy density required to ramp and maintain a composition disclosed herein comprising a photothermally active material at a temperature setpoint of 100°C for at least 2 minutes was reduced by at least 25%, such as by at least 30%, such as by at least 45%, such as by at least 50% compared to total energy density required to ramp and maintain the same composition that did not include a photothermally active material at the temperature setpoint for at least 2 minutes.

[0140] It was surprisingly and unexpectedly discovered that exposure of a composition comprising a blocked polyamine-containing compound, an acetoacetate-containing compound, and an epoxy-containing compound as disclosed herein to EMR generated by a laser and / or an LED resulted in sufficient heat generation to initiate cure of the composition. For example, exposure of a composition disclosed herein to EMR generated by a diode laser and having a wavelength of 900 nm to 1,080 nm, such as 960 nm to 985 nm, may require a total energy density to ramp and maintain the composition at a temperature of 100°C for at least 2 minutes of less than 550 J / cm2, such as less than 500 J / cm2, such as less than 400 J / cm2, such as less than 300 J / cm2, such as less than 200 J / cm2, such as less than 150 J / cm2.

[0141] It also was surprisingly and unexpectedly discovered that exposure of the composition comprising the blocked polyamine-containing compound, the acetoacetate- containing compound, and the epoxy-containing compound as disclosed herein to EMR generated by a laser and / or an LED accelerated the rate of cure compared to the same composition cured under ambient conditions. For example, exposure of such a composition to EMR generated by a laser and / or an LED and having a wavelength of 900 nm to 1,080 nm, such as 960 nm to 985 nm, may cure the composition following exposure to the EMR for a 30 second ramp from ambient to at least 100°C and held at such temperature for at least 2 minutes. This isdemonstrated, for example, by such coatings achieving 100 methyl ethyl ketone (MEK) double rubs (according to ASTM D5402-19) 45 minutes after EMR exposure. By comparison, the same composition cured under ambient conditions did not achieve 100 MEK double rubs 45 minutes after mixing the components, but rather achieved 100 MEK double rubs 24 hours after mixing the components, indicating that exposing a composition comprising acetoacetate to EMR generated by a laser and / or an LED accelerated cure of the composition following exposure to the EMR for a 30 second ramp from ambient to at least 100°C and held at such temperature for at least 2 minutes compared to the same composition cured under ambient conditions. This was a surprising and unexpected result.

[0142] Additionally, it was surprisingly and unexpectedly discovered that coating compositions comprising the blocked polyamine-containing compound, the aceto acetate - containing compound, the epoxy-containing compound, and a photothermally active material required a reduced total energy density to cure the composition compared to the same composition that did not include the photothermally active material. That is, the compositions disclosed herein comprising a photothermally active material required a reduced total energy density to ramp and maintain the composition at a temperature setpoint (defined in the Examples) compared to the total energy density required to ramp and maintain the same composition that did not include a photothermally active material at the temperature setpoint. For example, the total energy density required to ramp and maintain a composition disclosed herein comprising a photothermally active material at a temperature setpoint of 100°C for at least 2 minutes was reduced by at least 35%, such as by at least 40%, such as by at least 50% compared to total energy density required to ramp and maintain the same composition that did not include a photothermally active material at the temperature setpoint for at least 2 minutes.

[0143] It was surprisingly and unexpectedly discovered that exposure of a composition comprising a blocked polyamine-containing compound, an acetoacetate-containing compound, and a (meth)acrylate-containing compound as disclosed herein to EMR generated by a laser and / or an LED resulted in sufficient heat generation to initiate cure of the composition. For example, exposure of a composition disclosed herein to EMR generated by a diode laser and having a wavelength of 900 nm to 1,080 nm, such as 960 nm to 985 nm, may require a total energy density to ramp and maintain the composition at a temperature of 100°C for at least 2minutes of less than 500 J / cm2, such as less than 475 J / cm2, such as less than 400 J / cm2, such as less than 300 J / cm2, such as less than 200 J / cm2, such as less than 150 J / cm2.

[0144] It also was surprisingly and unexpectedly discovered that exposure of the composition comprising the blocked polyamine-containing compound, the acetoacetate- containing compound, and the (meth)acrylate-containing compound as disclosed herein to EMR generated by a laser and / or an LED accelerated the rate of cure compared to the same composition cured under ambient conditions. For example, exposure of such a composition to EMR generated by a laser and / or an LED and having a wavelength of 900 nm to 1,080 nm, such as 960 nm to 985 nm, may cure the composition following exposure to the EMR for a 30 second ramp from ambient to at least 100°C and held at such temperature for at least 2 minutes. This is demonstrated, for example, by such coatings achieving 100 methyl ethyl ketone (MEK) double rubs (according to ASTM D5402-19) 45 minutes after EMR exposure. By comparison, the same composition cured under ambient conditions did not achieve 100 MEK double rubs 45 minutes after mixing the components, but rather achieved 100 MEK double rubs 24 hours after mixing the components, indicating that exposing a composition comprising acetoacetate to EMR generated by a laser and / or an LED accelerated cure of the composition following exposure to the EMR for a 30 second ramp from ambient to at least 100°C and held at such temperature for at least 2 minutes compared to the same composition cured under ambient conditions. This was a surprising and unexpected result.

[0145] Additionally, it was surprisingly and unexpectedly discovered that coating compositions comprising the blocked polyamine-containing compound, the acetoacetate - containing compound, the (meth)acrylate-containing compound, and a photothermally active material required a reduced total energy density to cure the composition compared to the same composition that did not include the photothermally active material. That is, the compositions disclosed herein comprising a photothermally active material required a reduced total energy density to ramp and maintain the composition at a temperature setpoint (defined in the Examples) compared to the total energy density required to ramp and maintain the same composition that did not include a photothermally active material at the temperature setpoint. For example, the total energy density required to ramp and maintain a composition disclosed herein comprising a photothermally active material at a temperature setpoint of 100°C for at least 2 minutes was reduced by at least 30%, such as by at least 35%, such as by at least 40%compared to total energy density required to ramp and maintain the same composition that did not include a photothcrmally active material at the temperature setpoint for at least 2 minutes.

[0146] It was surprisingly and unexpectedly discovered that exposure of a composition comprising a blocked polyamine-containing compound, an acetoacetate-containing compound, an epoxy-containing compound, and a (meth)acrylate-containing compound as disclosed herein to EMR generated by a laser and / or an LED resulted in sufficient heat generation to initiate cure of the composition. For example, exposure of a composition disclosed herein to EMR generated by a diode laser and having a wavelength of 900 nm to 1,080 nm, such as 960 nm to 985 nm, may require a total energy density to ramp and maintain the composition at a temperature of 100°C for at least 2 minutes of less than 500 J / cm2, such as less than 450 J / cm2, such as less than 400 J / cm2, such as less than 300 J / cm2, such as less than 200 J / cm2, such as less than 150 J / cm2.

[0147] It also was surprisingly and unexpectedly discovered that exposure of the composition comprising the blocked polyamine-containing compound, the acetoacetate- containing compound, the epoxy-containing compound, and the (meth)acrylate-containing compound as disclosed herein to EMR generated by a laser and / or an LED accelerated the rate of cure compared to the same composition cured under ambient conditions. For example, exposure of such a composition to EMR generated by a laser and / or an LED and having a wavelength of 900 nm to 1,080 nm, such as 960 nm to 985 nm, may cure the composition following exposure to the EMR for a 30 second ramp from ambient to at least 100°C and held at such temperature for at least 2 minutes. This is demonstrated, for example, by such coatings achieving 100 methyl ethyl ketone (MEK) double rubs (according to ASTM D5402-19) 45 minutes after EMR exposure. By comparison, the same composition cured under ambient conditions did not achieve 100 MEK double rubs 45 minutes after mixing the components, but rather achieved 100 MEK double rubs 24 hours after mixing the components, indicating that exposing a composition comprising acetoacetate to EMR generated by a laser and / or an LED accelerated cure of the composition following exposure to the EMR for a 30 second ramp from ambient to at least 100°C and held at such temperature for at least 2 minutes compared to the same composition cured under ambient conditions. This was a surprising and unexpected result.

[0148] Additionally, it was surprisingly and unexpectedly discovered that coating compositions comprising the blocked polyamine-containing compound, the acetoacetate- containing compound, the epoxy-containing compound, the (meth)acrylate-containingcompound, and a photothermally active material required a reduced total energy density to cure the composition compared to the same composition that did not include the photothermally active material. That is, the compositions disclosed herein comprising a photothermally active material required a reduced total energy density to ramp and maintain the composition at a temperature setpoint (defined in the Examples) compared to the total energy density required to ramp and maintain the same composition that did not include a photothermally active material at the temperature setpoint. For example, the total energy density required to ramp and maintain a composition disclosed herein comprising a photothermally active material at a temperature setpoint of 100°C for at least 2 minutes was reduced by at least 30%, such as by at least 35%, such as by at least 40% compared to total energy density required to ramp and maintain the same composition that did not include a photothermally active material at the temperature setpoint for at least 2 minutes.

[0149] These results surprisingly and unexpectedly demonstrate that exposure of the compositions to EMR generated by a laser and / or an LED may provide cure on demand without negatively impacting mechanical properties of the resulting coating. Thus, it was surprisingly and unexpectedly demonstrated that curing the compositions disclosed herein by exposure to EMR generated by a laser and / or an LED may be advantageous to achieve cure on demand and result in a mechanically robust coating.Substrates

[0150] Substrates useful for the methods disclosed herein may be selected from a wide variety of substrates and combinations thereof. Non-limiting examples of substrates include vehicles including automotive substrates, industrial substrates, marine substrates and components such as ships, vessels, and on-shore and off-shore installations, storage tanks such as fuel tanks, packaging substrates, pressurized cabins, architectural substrates, aircraft and aerospace components, batteries and battery components, bus bars, metal wires, electrical and aviation equipment, structural joints and rivets, caps, copper or aluminum conductors, nickel conductors, wood flooring and furniture, fasteners, coiled metals, heat exchangers, vents, an extrusion, roofing, walls, wheels, grates, belts, conveyors, grain or seed silos, wire mesh, bolts or nuts, a screen or grid, HVAC equipment such as environmental control systems, frames, tanks, cords, wires, a rail car, furniture, appliances, apparel, a bulkhead, pipes, transformers, toolboxes, grills, medical equipment, doors, windows, a well, cabinets, pylons, electronics and electroniccomponents including housings and circuit boards, glass, sports equipment, including golf balls, large and / or fixed objects such as stadiums, buildings, bridges, containers such as a food and beverage containers, and the like.

[0151] “Vehicle” as used herein refers to in its broadest sense all types of vehicles, such as, but not limited to, cars, trucks, buses, tractors, harvesters, heavy duty equipment, vans, golf carts, motorcycles, bicycles, railcars, subway cars, airplanes, drones, VTOLs, helicopters, ships, vessels, boats of all sizes and the like. A vehicle can include civilian, commercial and military aircraft or land vehicles, such as those listed above and those used in land-based defense (tanks, armored vehicles, and the like). A vehicle can include autonomous and / or unmanned vehicles.

[0152] It will also be appreciated that the substrates of the present disclosure can form a part of a structure. The compositions of the present disclosure can be used in any article of manufacture, such as a vehicle or a structure. “Structure” as used herein refers to a any part of a building, stadium, bridge, transportation infrastructure, oil rig, oil platform, water tower, power line tower, support structures, wind turbines, storage tanks, nuclear plants, walls, piers, docks, levees, dams, shipping containers, trailers, and any metal structure that is exposed to a corrosive environment.

[0153] The substrates, including any of the substrates previously described, can be metallic or non-metallic. Metallic substrates may include both flexible and rigid metal substrates such as tin, iron, steel, and alloys thereof. Non-limiting examples of useful steel materials include cold rolled steel, nickel plated cold rolled steel, hot rolled steel, galvanized (zinc coated) steel, electrogalvanized steel, hot-dipped galvanized steel, galvannealed steel, zinc compounds, zinc alloys, galvalume, steel plated with zinc alloy, stainless steel, cadmium plated steel, pickled steel, zinc-aluminum-magnesium alloy coated steel, aluminum plated steel, aluminum alloy plated steel, steel coated with a zinc-aluminum alloy, or combinations thereof. Metallic substrates may include zinc-aluminum alloys, aluminum, aluminum alloys, magnesium, magnesium alloys, nickel, nickel plating, bronze, tinplate, clad, titanium, brass, copper, silver, gold, 3-D printed metals, cast or forged metals and alloys, or combinations thereof. Aluminum alloys, such as those, for example, of the 1XXX, 2XXX, 3XXX, 4XXX, 5XXX, 6XXX, 7XXX, or 8XXX series as well as clad aluminum alloys and cast aluminum alloys, such as those, for example, of the A356, 1XX.X, 2XX.X, 3XX.X, 4XX.X, 5XX.X, 6XX.X, 7XX.X, or 8XX.X series also may be used as the substrate. The substrate also may comprise, for example,magnesium, such as magnesium alloys of the AZ31B, AZ91C, AM60B, or EV31 A series, titanium and / or titanium alloys, such as those of grades 1-36 including H grade variants, copper and copper alloys, or other non-ferrous metals, as well as alloys of these materials.

[0154] Non-metallic substrates include polymeric, plastic, polyester, polyolefin, polyamide, cellulosic, polystyrene, polyacrylic, poly(ethylene naphthalate), polypropylene, polyethylene, nylon, ethylene vinyl alcohol (EVOH), polylactic acid, other “green” polymeric substrates, poly(ethyleneterephthalate) (PET), polycarbonate, engineering polymers such as poly(etheretherketone) (PEEK), polycarbonate acrylobutadiene styrene (PC / ABS), polyamide, wood, veneer, wood composite, particle board, medium density fiberboard, cement, stone, glass, paper, cardboard, textiles, leather both synthetic and natural, composite substrates such as fiberglass composites or carbon fiber composites such as fiberglass -epoxy composites or carbon fiber-epoxy composites, 3-D printed polymers and composites, synthetic fibers and the like, such as those available as Kevlar® materials. The shape of the substrate can be in the form of a sheet, plate, bar, rod, or any shape desired.

[0155] The substrate may comprise a bare substrate or the substrate may undergo various treatments prior to application of the composition. For instance, the substrate can be mechanically and / or chemically treated, such as alkaline cleaned, deoxidized, mechanically cleaned and / or abraded, ultrasonically cleaned, solvent wiped, roughened, plasma cleaned or etched, exposed to chemical vapor deposition, treated with an adhesion promoter, plated, anodized, annealed, cladded, or any combination thereof prior to application of the composition. The substrate can be treated using any of the previously described methods prior to application of the composition such as by dipping the substrate in a cleaner and / or deoxidizer bath prior to applying the composition. The substrate can also be plated prior to applying the composition. As used herein, “plating” refers to depositing a metal over a surface of the substrate.Definitions

[0156] For purposes of this detailed description, it is to be understood that the disclosure may assume alternative variations, except where expressly specified to the contrary.

[0157] The numerical values set forth in the 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.

[0158] Also, 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.

[0159] As used herein, “including,” “containing” and like terms are understood in the context of this application to be synonymous with “comprising” and are therefore open-ended and do not exclude the presence of additional undescribed or unrecited elements, materials, or ingredients. As used herein, “consisting of’ is understood in the context of this application to exclude the presence of any unspecified element, material, or ingredient. As used herein, “consisting essentially of’ is understood in the context of this application to include the specified elements, materials, or ingredients and those that do not materially affect the basic and novel characteristics of what is being described.

[0160] 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.

[0161] As used herein, the terms “on,” “onto,” “applied on,” “applied onto,” “formed on,” “deposited on,” “deposited onto,” and the like mean formed, overlaid, deposited, or provided on, but not necessarily in contact with, a substrate surface. For example, a composition “applied onto” a substrate surface does not preclude the presence of one or more intervening coating layers or films of the same or different composition located between the composition and the substrate surface.

[0162] As used herein, a “composition” refers to a solution, mixture, or dispersion that is capable of forming a coating on a substrate surface. “Coating” as used herein includes films, layers, and the like.

[0163] As used herein, a “sealant composition” refers to a composition that forms a sealant in its cured state.

[0164] As used herein, the term “sealant” refers to a coating that has the ability to resist atmospheric conditions, such as moisture and temperature, and at least partially block the transmission of materials, such as water, fuel, liquids, and gases. The compositions disclosed herein may be useful, for example, as aerospace sealants and linings for fuel tanks.

[0165] As used herein, a “gap filler composition” refers to a composition that forms a gap filler in its cured state.

[0166] As used herein, a “gap filler” refers to a coating that fills a gap between two substrates in order to eliminate air voids, such as filling a crack, a hole, or a butt joint. As used herein, “butt joint” refers to a joint formed by two surfaces abutting at right angles.

[0167] As used herein, an “adhesive composition” refers to a composition that forms an adhesive in its cured state.

[0168] As used herein, an “adhesive” refers to a coating that produces a load-bearing joint.

[0169] As used herein, a “pottant composition” refers to a composition that, when cured, forms a pottant.

[0170] As used herein, a “pottant” refers to an encapsulant.

[0171] As used herein, a “pre-preg” refers to a composition pre-impregnating reinforcement fibers prior to cure.

[0172] As used herein, a “liquid shim composition” refers to a composition that, when cured, forms a liquid shim.

[0173] As used herein, a “liquid shim” refers to a coating that eliminates gaps between substrate surfaces.

[0174] As used herein, “ambient” conditions generally refer to room temperature (e.g., 25 °C) and humidity conditions or temperature and humidity conditions that are typically found in the area in which the composition is applied to a substrate, e.g., at 10°C to 40°C and 5% to 80% relative humidity, while slightly thermal conditions are temperatures that are slightly above ambient temperature, but are generally below the curing temperature for the composition (i.e., in other words, at temperatures and humidity conditions below which the reactive components will readily react and cure, e.g., > 40°C and less than 220°C at 20% to 80% relative humidity).

[0175] As used herein, “total solids” refers to the non-volatile content of the composition, i.e., materials which will not volatilize when heated to 110°C and standard atmospheric pressure (1 atm) for 60 minutes.

[0176] As used herein, the term “cure,” “curing,” and similar terms, mean that the components that form the composition begin to crosslink (i.e., interact and / or react) to form a coating or a bond or a surface that is tack free. In the case of a 2K composition, the compositionbegins to cure when the components of the composition are mixed, resulting in the reaction of the reactive functional groups of the components of the composition and / or the physical interaction of the components of the composition.

[0177] As used herein, “tack free” means a material that is dry to the touch on the surface and that does not leave a residue when touched (see AS5127 / ID).

[0178] As used herein, a dash (“ — ”) that is not between two letters or symbols is used to indicate a point of bonding for a substituent or between two atoms. For example, — CONH2 refers to an amide functional group that is bonded to another chemical moiety through the carbon atom.

[0179] As used herein, “alkoxy” refers to a — OR group where R is alkyl or aromatic as defined herein. Non-limiting examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, and n-butoxy.

[0180] As used herein, “alkyl” refers to an aliphatic hydrocarbon group which may be straight or branched. Branched means that one or more alkyl groups such as methyl, ethyl or propyl, are attached to a linear alkyl chain. “Alkyl” may be unsubstituted or optionally substituted by one or more substituents which may be the same or different, each substituent being independently selected from the group consisting of halo, alkyl, aryl, cycloalkyl, cyano, hydroxy, alkoxy, alkylthio, amino, — NH(alkyl), — NH(cycloalkyl), — N(alkyl)2, carboxy and — C(O)O-alkyl. Non-limiting examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl and t-butyl.

[0181] As used herein, unless indicated otherwise, the term “substantially free” means that a particular material is not purposefully added to a mixture or composition, respectively, and is present only as an impurity in a trace amount of less than 0.05% by weight based on a total weight of the mixture or composition, respectively. As used herein, unless indicated otherwise, the term “essentially free” means that a particular material is present only in an amount of less than 0.01% by weight based on a total weight of the mixture or composition, respectively. As used herein, unless indicated otherwise, the term “completely free” means that a mixture or composition, respectively, does not comprise a particular’ material, i.e., the mixture or composition comprises 0% by weight of such material.

[0182] In view of the foregoing description the present disclosure thus relates to the following Aspects 1 to 106 without being limited thereto.

[0183] Aspect 1. A method of curing a composition comprising: exposing the composition to electromagnetic radiation (EMR) generated by a laser and / or a light emitting diode (LED) to cure the composition; wherein the composition comprises (a) an acetoacetate-containing compound and (b) a blocked polyamine-containing compound.

[0184] Aspect 2. The method of aspect 1, wherein the composition further comprises (c) an epoxy-containing compound and / or (d) a (meth)acrylate-containing compound.

[0185] Aspect 3. The method of aspect 1 or aspect 2, wherein the EMR comprises visible light and / or near infrared light.

[0186] Aspect 4. The method of any of the preceding aspects, wherein the EMR comprises a wavelength of at least 300 nm, such as at least 900 nm.

[0187] Aspect 5. The method of any of the preceding aspects, wherein the EMR comprises a wavelength of at least 960 nm.

[0188] Aspect 6. The method of any of the preceding aspects, wherein the EMR comprises a wavelength of no more than 2,500 nm, such as no more than 1,500 nm.

[0189] Aspect 7. The method of any of the preceding aspects, wherein the EMR comprises a wavelength of no more than 1,080 nm, such as no more than 985 nm.

[0190] Aspect 8. The method of any of aspects 1 to 4, and 6, wherein the EMR comprises a wavelength of 300 nm to 2,500 nm, such as 300 nm to 1,500 nm.

[0191] Aspect 9. The method of any of aspects 1 to 4 and 6 to 8, wherein the EMR comprises a wavelength of 900 nm to 1,080 nm.

[0192] Aspect 10. The method of any of the preceding aspects, wherein the EMR comprises a wavelength of 960 nm to 985 nm.

[0193] Aspect 11. The method of any of the preceding aspects, wherein the EMR is generated as a continuous wave, a quasi-continuous wave, and / or a pulsed wave.

[0194] Aspect 12. The method of any of the preceding aspects, wherein the EMR is directional.

[0195] Aspect 13. The method of any of the preceding aspects, wherein the EMR comprises monochromatic light and / or polychromatic light.

[0196] Aspect 14. The method of any of the preceding aspects, wherein the EMR is coherent.

[0197] Aspect 15. The method of any of the preceding aspects, wherein the laser and / or the LED is defocused.

[0198] Aspect 16. The method of any of the preceding aspects, wherein the laser generates diffuse EMR, divergent EMR, and / or collimated EMR.

[0199] Aspect 17. The method of any of the preceding aspects, wherein the laser comprises a solid-state laser, a gas laser, a semiconductor (diode) laser, a fiber laser, a dye laser, and / or a high harmonic generation laser such as a frequency-doubled or a frequency-tripled laser.

[0200] Aspect 18. The method of any of the preceding aspects, wherein the laser and / or the LED is configured as a single diode, a diode laser bar, and / or a diode laser stack.

[0201] Aspect 19. The method of any of the preceding aspects, wherein the laser has a wall plug efficiency of at least 30 percent, such as at least 50 percent.

[0202] Aspect 20. The method of any of the preceding aspects, wherein the laser has a wall plug efficiency of at least 60 percent, such as at least 80 percent.

[0203] Aspect 21. The method of any of aspects 1 to 19, wherein the laser has a wall plug efficiency of 30 percent to 80 percent, such as 50 percent to 80 percent.

[0204] Aspect 22. The method of any of the preceding aspects, wherein the laser has a wall plug efficiency of 60 percent to 80 percent.

[0205] Aspect 23. The method of any of aspects 1 to 19, wherein the laser has a wall plug efficiency of 30 percent to 50 percent.

[0206] Aspect 24. The method of any of the preceding aspects, wherein a unit comprising the laser and / or the LED further comprises adaptive optics such as optics to tailor focal intensity and / or a wide area distribution of the EMR.

[0207] Aspect 25. The method of aspect 24, wherein the unit comprising the laser and / or the LED further comprises an amplifier, a temperature sensor, and / or an IR sensor.

[0208] Aspect 26. The method of aspect 25, wherein the temperature sensor controls a temperature of the composition, a substrate temperature, and / or a ramp rate.

[0209] Aspect 27. The method of any of the preceding aspects, wherein the laser and / or the LED comprises an industrial-sized laser and / or LED.

[0210] Aspect 28. The method of any of aspects 1 to 26, wherein the laser and / or the LED comprises a portable device and / or a hand-held device.

[0211] Aspect 29. The method of any of the preceding aspects, wherein the laser and / or the LED is a robotically guided device and / or wherein the laser is connected to a robotically guided device.

[0212] Aspect 30. The method of any of the preceding aspects, wherein the composition further comprises a photothermally active material.

[0213] Aspect 31. The method of aspect 30, wherein the photothermally active material comprises carbon black.

[0214] Aspect 32. The method of aspect 30 or aspect 31 , wherein the composition comprises the photothermally active material in an amount of at least 0.001 percent by weight based on total solids weight of the composition, such as at least 0.01 percent by weight.

[0215] Aspect 33. The method of any of aspects 30 to 32, wherein the composition comprises the photothermally active material in an amount of no more than 10 percent by weight based on total solids weight of the composition, such as no more than 7 percent by weight.

[0216] Aspect 34. The method of any of aspects 30 to 33, wherein the composition comprises the photothermally active material in an amount of 0.001 percent by weight to 10 percent by weight based on total solids weight of the composition, such as 0.01 percent by weight to 7 percent by weight.

[0217] Aspect 35. The method of any of the preceding aspects, wherein the acetoacetate-containing compound comprises a small molecule and / or a polymer.

[0218] Aspect 36. The method of any of the preceding aspects, wherein the acetoacetate-containing compound comprises an acetoacetate functionality of 2 to 10, such as 2 to 5.

[0219] Aspect 37. The method of any of the preceding aspects, wherein the acetoacetate-containing compound comprises an Mn of at least 216 g / mol as determined by gas permeation chromatography, such as at least 500 g / mol.

[0220] Aspect 38. The method of any of the preceding aspects, wherein the acetoacetate-containing compound comprises an Mn of no more than 50,000 g / mol as determined by gas permeation chromatography, such as no more than 40,000 g / mol.

[0221] Aspect 39. The method of any of the preceding aspects, wherein the acetoacetate-containing compound comprises an Mn of 216 g / mol to 50,000 g / mol as determined by gas permeation chromatography, such as 500 g / mol to 40,000 g / mol.

[0222] Aspect 40. The method of any of the preceding aspects, wherein the composition comprises the acetoacetate-containing composition in an amount of at least 1% by weight based on total solids weight of the composition, such as at least 5% by weight.

[0223] Aspect 41. The method of any of the preceding aspects, wherein the composition comprises the acetoacetate-containing composition in an amount of no more than 95% by weight based on total solids weight of the composition, such as no more than 85% by weight.

[0224] Aspect 42. The method of any of the preceding aspects, wherein the composition comprises the acetoacetate-containing composition in an amount of 1% by weight to 95% by weight based on total solids weight of the composition, such as 5% by weight to 85% by weight.

[0225] Aspect 43. The method of any of the preceding aspects, wherein the blocked polyamine-containing compound comprises an aliphatic compound and / or an aromatic compound.

[0226] Aspect 44. The method of any of the preceding aspects, wherein the composition comprises the blocked polyamine-containing composition in an amount of at least 1% by weight based on total solids weight of the composition, such as at least 5% by weight.

[0227] Aspect 45. The method of any of the preceding aspects, wherein the composition comprises the blocked polyamine-containing composition in an amount of no more than 95% by weight based on total solids weight of the composition, such as no more than 85% by weight.

[0228] Aspect 46. The method of any of the preceding aspects, wherein the composition comprises the blocked polyamine-containing composition in an amount of 1% by weight to 95% by weight based on total solids weight of the composition, such as 5% by weight to 85% by weight.

[0229] Aspect 47. The method of any of aspects 2 to 46, wherein the epoxy-containing compound comprises a monoepoxide, a diepoxide, or a polyepoxide.

[0230] Aspect 48. The method of any of aspects 2 to 47, wherein the epoxy-containing compound comprises a monomer, a small molecule, and / or a polymer.

[0231] Aspect 49. The method of any of aspects 2 to 48, wherein the epoxy-containing compound comprises an epoxy equivalent weight of at least 90 g / eq, such as at least 188 g / eq.

[0232] Aspect 50. The method of any of aspects 2 to 49, wherein the epoxy-containing compound comprises an epoxy equivalent weight of no more than 2,000 g / eq, such as no more than 500 g / eq.

[0233] Aspect 51. The method of any of aspects 2 to 50, wherein the epoxy-containing compound comprises an epoxy equivalent weight of 90 g / eq to 2,000 g / eq, such as 188 g / eq to 500 g / eq.

[0234] Aspect 52. The method of any of aspects 2 to 51, wherein the (meth)acrylate- containing compound comprises 2 to 20 olefinic double bonds.

[0235] Aspect 53. The method of any of aspects 2 to 52, wherein the (meth)acrylate- containing compound comprises a di(meth)acrylate, a tri(meth)acrylate, and / or a tetra(meth) acrylate .

[0236] Aspect 54. The method of any of the preceding aspects, wherein the composition further comprises an accelerator, an additive, a filler, and / or a solvent.

[0237] Aspect 55. The method of aspect 54, wherein the accelerator is a latent, blocked, and / or encapsulated accelerator.

[0238] Aspect 56. The method of aspect 54 or aspect 55, wherein the composition comprises the accelerator in an amount of at least 0.01% by weight based on total solids weight of the composition, such as at least 0.1 % by weight.

[0239] Aspect 57. The method of any of aspects 54 to 56, wherein the composition comprises the accelerator in an amount of no more than 10% by weight based on total solids weight of the composition, such as at least 5% by weight.

[0240] Aspect 58. The method of any of aspects 54 to 57, wherein the composition comprises the accelerator in an amount of 0.01% by weight to 10% by weight based on total solids weight of the composition, such as 0.1% by weight to 5% by weight.

[0241] Aspect 59. The method of any of aspects 54 to 58, wherein the additive comprises a rheology modifier, a reactive diluent, a non-reactive diluent, a dispersant, a tackifier, a thermoplastic polymer, a surface-active agent, a flame retardant, a corrosion inhibitor, a UV stabilizer, a hindered amine light stabilizer (HALS), a colorant, a tint, a plasticizer, an adhesion promoter, an antioxidant, a silane, a silane terminated polymer, a silyl terminated polymer, and / or a moisture scavenger.

[0242] Aspect 60. The method of any of aspects 54 to 59, wherein the composition comprises the additive in an amount of at least 0.01% by weight based on total solids weight of the composition, such as at least 0.1% by weight.

[0243] Aspect 61. The method of any of aspects 54 to 60, wherein the composition comprises the additive in an amount of no more than 15% by weight based on total solids weight of the composition, such as at least 5% by weight.

[0244] Aspect 62. The method of any of aspects 54 to 61, wherein the composition comprises the additive in an amount of 0.01% by weight to 15% by weight based on total solids weight of the composition, such as 0.1% by weight to 5% by weight.

[0245] Aspect 63. The method of any of aspects 54 to 62, wherein the composition comprises the filler in an amount of at least 0.1% by weight based on total solids weight of the composition, such as at least 1% by weight.

[0246] Aspect 64. The method of any of aspects 54 to 63, wherein the composition comprises the filler in an amount of no more than 90% by weight based on total solids weight of the composition, such as no more than 80% by weight.

[0247] Aspect 65. The method of any of aspects 54 to 64, wherein the composition comprises the filler in an amount of 0.1% by weight to 90% by weight based on total solids weight of the composition, such as 1% by weight to 80% by weight.

[0248] Aspect 66. The method of any of aspects 54 to 65, wherein the composition comprises the solvent in an amount of at least 5% by weight based on total solids weight of the composition, such as at least 20% by weight.

[0249] Aspect 67. The method of any of aspects 54 to 66, wherein the composition comprises the solvent in an amount of no more than 80% by weight based on total solids weight of the composition, such as no more than 40% by weight.

[0250] Aspect 68. The method of any of aspects 54 to 67, wherein the composition comprises the solvent in an amount of 5% by weight to 80% by weight based on total solids weight of the composition, such as 20% by weight to 40% by weight.

[0251] Aspect 69. The method of any of the preceding aspects, wherein the composition has a total solids content of at least 20% by weight based on total weight of the composition, such as at least 60% by weight.

[0252] Aspect 70. The method of any of the preceding aspects, wherein the composition has a total solids content of up to 100% by weight based on total weight of the composition.

[0253] Aspect 71. The method of any of the preceding aspects, wherein the composition has a total solids content of 20% by weight to 100% by weight based on total weight of the composition, such as 60% by weight to 100% by weight.

[0254] Aspect 72. The method of any of aspects 2 to aspect 71, wherein the composition has an equivalent ratio of (i) acetoacetate functional groups, epoxy functional groups, and (meth) acrylate functional groups to (ii) blocked amine functional groups of at least 0.5:1, such as at least 0.75:1.

[0255] Aspect 73. The method of any of aspects 2 to aspect 72, wherein the composition has an equivalent ratio of (i) acetoacetate functional groups, epoxy functional groups, and (meth)acrylate functional groups to (ii) blocked amine functional groups of no more than 1.5:1, such as no more than 1.25:1.

[0256] Aspect 74. The method of any of aspects 2 to aspect 73, wherein the composition has an equivalent ratio of (i) acetoacetate functional groups, epoxy functional groups, and (meth) acrylate functional groups to (ii) blocked amine functional groups of 0.5:1 to 1.5:1, such as 0.75:1 to 1.25:1.

[0257] Aspect 75. The method of any of the preceding aspects, wherein the composition is substantially free, essentially free, or completely free of a photopolymerizable initiator.

[0258] Aspect 76. The method of any of the preceding aspects, wherein the composition is formulated as a sealant composition, an adhesive composition, a gap filler composition, a pottant composition, a prepreg, and / or a liquid shim composition.

[0259] Aspect 77. The method of any of the preceding aspects, wherein the composition is formulated as a IK composition, a 2K composition, and / or a higher-component composition.

[0260] Aspect 78. The method of any of the preceding aspects, comprising applying the composition to a surface of a substrate, such as by extruding, pressing, grouting, caulking, spreading, brushing, rolling, troweling, dipping, and / or spraying.

[0261] Aspect 79. The method of any of the preceding aspects, wherein the composition is exposed to the EMR for at least 2 minutes.

[0262] Aspect 80. The method of any of the preceding aspects, wherein the composition is exposed to the EMR at an intensity of at least 0.01 W / cm2, such as at least 0.1 W / cm2.

[0263] Aspect 81. The method of any of the preceding aspects, wherein the composition is exposed to the EMR at an intensity of at least 0.2 W / cm2.

[0264] Aspect 82. The method of any of the preceding aspects, wherein the composition is exposed to the EMR at an intensity of no more than 108W / cm2, such as no more than 106W / cm2.

[0265] Aspect 83. The method of any of the preceding aspects, wherein the composition is exposed to the EMR at an intensity of no more than 104W / cm2, such as no more than 102W / cm2.

[0266] Aspect 84. The method of any of the preceding aspects, wherein the composition is exposed to the EMR at an intensity of no more than 15 W / cm2, such as no more than 12 W / cm2.

[0267] Aspect 85. The method of any of the preceding aspects, wherein the composition is exposed to the EMR at an intensity of 0.01 W / cm2to 108W / cm2, such as 0.1 W / cm2to 106W / cm2.

[0268] Aspect 86. The method of any of aspects 1 to 81 and 83, wherein the composition is exposed to the EMR at an intensity of 0.1 W / cm2to 104W / cm2, such as 0.1 W / cm2to 102W / cm2.

[0269] Aspect 87. The method of any of aspects 1 to 81 and 84 to 86, wherein the composition is exposed to the EMR at an intensity of 0.1 W / cm2to 15 W / cm2, such as 0.2 W / cm2to 12 W / cm2.

[0270] Aspect 88. The method of any of aspects 78 to 87, comprising cleaning and / or deoxidizing the substrate surface.

[0271] Aspect 89. The method of any of aspects 78 to 88, comprising coating the substrate surface with a coating composition in addition to the composition, such as a pretreatment composition, an electrodepo sitable coating composition, a primer coating composition, a basecoat coating composition, and / or a topcoat coating composition.

[0272] Aspect 90. The method of any of aspects the preceding aspects, wherein the substrate comprises a fixed structure.

[0273] Aspect 91. The method of any of aspects 78 to 90, comprising applying the composition to a damaged portion of the surface of the substrate.

[0274] Aspect 92. The method of any of aspects 78 to 91, wherein the surface comprises a pre-existing coating, and wherein the pre-existing coating is at least partially removed prior to the applying.

[0275] Aspect 93. The method of any of aspects 78 to 92, wherein a temperature of the surface of the substrate does not exceed 121°C upon exposure to the EMR.

[0276] Aspect 94. The method of any of aspects 78 to 93, further comprising contacting a surface of a second substrate to the composition such that the composition is between the surface of the substrate and the surface of the second substrate.

[0277] Aspect 95. The method of any of the preceding aspects, wherein a total energy density of less than 550 J / cm2is required to cure the coating, such as less than 500 J / cm2.

[0278] Aspect 96. The method of any of the preceding aspects, wherein a total energy density of less than 475 J / cm2is required to cure the coating, such as less than 450 J / cm2.

[0279] Aspect 97. The method of any of the preceding aspects, wherein a total energy density of less than 400 J / cm2is required to cure the coating, such as less than 300 J / cm2.

[0280] Aspect 98. The method of any of the preceding aspects, wherein a total energy density of less than 200 J / cm2is required to cure the coating, such as less than 175 J / cm2.

[0281] Aspect 99. The method of any of the preceding aspects, wherein a total energy density of less than 150 J / cm2is required to cure the coating.

[0282] Aspect 100. The method of any of aspects 30 to 99, wherein a total energy density required to cure the composition was reduced by at least 25% compared to a total energy density required to cure a composition that did not comprise the photothermally active material, such as reduced by at least 30%.

[0283] Aspect 101. The method of any of aspects 30 to 100, wherein a total energy density required to cure the composition was reduced by at least 35% compared to a total energy density required to cure a composition that did not comprise the photothermally active material, such as reduced by at least 40%.

[0284] Aspect 102. The method of any of aspects 30 to 101, wherein a total energy density required to cure the composition was reduced by at least 45% compared to a total energy density required to cure a composition that did not comprise the photothermally active material, such as reduced by at least 50%.

[0285] Aspect 103. The method of any of aspects 26 to 102, wherein a temperature of the substrate following exposure to the EMR is below a heat deflection temperature of the substrate.

[0286] Aspect 104. A substrate comprising a coating formed from the composition cured by the method of any of the preceding aspects.

[0287] Aspect 105. The substrate of aspect 104, wherein the coating comprises a sealant, an adhesive, a gap filler, a pottant, a prepreg, and / or a liquid shim.

[0288] Aspect 106. The substrate of aspect 104 or aspect 105, wherein the coating achieved 100 MEK double rubs, tested according to ASTM D5402-19, 45 minutes after the exposure to the EMR.

[0289] Illustrating the disclosure are the following examples, which, however, are not to be considered as limiting the disclosure to their details.EXAMPLESExample A - Solventborne Ketimine Clear BaseTable 11The epoxy / ketimine resin was made as described in U.S. Patent No. 5,288,802, col. 10, 1. 19 - col. 11, 1. 6.2Adhesion promoter

[0290] The solventborne ketimine clear base (Example A) was prepared using the components in the amounts provided in Table 1. Components 1 and 2 were weighed into a 16 oz. glass jar, then hand mixed until homogeneous. Then, Components 3 and 4 were added, in order, and the mixture was hand mixed until homogeneous.Example B - Solventborne Ketimine White BaseTable 23Dispersant4Titanium dioxide

[0291] The solventborne ketimine white base (Example B) was prepared using the components in the amounts provided in Table 2. Components 1-4 were weighed into a 16 oz. glass jar. 2.0 mm aluminum oxide grind media was added to the glass jar in an amount of 50% by weight based on total weight of Components 1-4. The glass jar was placed onto a Lau Disperser DAS 200 (Lau GmbH, Germany) for 90 minutes until a Hegman grind of 8 was reached. Components 5 and 6 were added, in order, and the jar was placed back on the Lau disperser for 10 minutes. The grind media was then filtered through a 125-micron mesh filter into a clean 16 oz. jar.Example C - Solventborne Ketimine Black BaseTable 3

[0292] The solventborne ketimine black base (Example C) was prepared using the components in the amounts provided in Table 3. Components 1-4 were weighed into a 16 oz. glass jar. 2.0 mm aluminum oxide grind media was added to the glass jar in an amount of 50% by weight based on total weight of Components 1-4. The glass jar was placed onto the LauDisperser DAS 200 (Lau GmbH, Germany) for 90 minutes until a Hegman grind of 6.5 was reached. Components 5 and 6 were added, in order, and the jar was placed back on the Lau disperser for 10 minutes. The grind media was then filtered through a 125-micron mesh filter into a clean 16 oz. jar.Table 4

[0293] The tinted clear base (Example D) was prepared by adding Components 1 and 2 to a glass jar in the amounts provided in Table 4 and hand stirring until homogenous.Table 5Example E - Tinted White BaseComponent Amount (g)Example B - White Base 99.10Example C - Black Base 0.99

[0294] The tinted white base (Example E) was prepared by adding Components 1 and 2 to a glass jar in the amounts provided in Table 5 and hand stirring until homogenous.Table 6Example F - Acetoacetate Hardener5The acetoacetate polyester was made as described in U.S. Patent No. 5,288,802, col. 9, 1. 40 - col. 10, 1.16.

[0295] The acetoacetate hardener (Example F) was prepared by adding Components 1 to 3 to a glass jar in the amounts provided in Table 6 and hand stirring until homogenous.Table 7Example G - Epoxy + Acetoacetate Hardener

[0296] The epoxy and acetoacetate hardener (Example G) was prepared by adding Components 1 to 4 to a glass jar in the amounts provided in Table 7 and hand stirring until homogenous.Table 8Example H - Acrylate + Acetoacetate Hardener

[0297] The acrylate and acetoacetate hardener (Example H) was prepared by adding Components 1 to 4 to a glass jar in the amounts provided in Table 8 and hand stirring until homogenous.Table 9Example - Epoxy + Acrylate + Acetoacetate HardenerComponent Supplier Amount (g)

[0298] The epoxy, acrylate, and acetoacetate hardener (Example I) was prepared by adding Components 1 to 5 to a glass jar in the amounts provided in Table 9 and hand stirring until homogenous.Preparation of Samples 1 to 20

[0299] Samples 1 to 20 were prepared by first weighing the respective base (Examples A - E) in the amounts provided in Tables 10 to 13 into a 20 mL glass jar. Then, the corresponding amount of hardener (Examples F - 1) was added to a separate 20 mL glass jar.Table 10: Samples 1 to 5: Base + Acetoacetate Hardener CompositionsTable 11: Samples 6 to 10: Base + Epoxy / Acetoacetate Hardener CompositionsTable 12: Samples 11 to 15: Base + Acrylate / Acetoacetate Hardener CompositionsTable 13: Samples 16 to 20: Base + Epoxy / Acrylate / Acetoacetate Hardener Compositions

[0300] Immediately prior to drawdown of the samples, the contents of the respective base and hardener glass jars were combined and hand mixed until homogenous. A drawdown of each sample was made using an 8 mil Byk-Gardner drawdown bar (targeting 1.5 - 3.0 mil dry film thickness) on a B1000 / P99X pretreated (ACT Item #40821, ACT Test Panels, LLC) then powder coated with PCTA89105 RAL 9010 Pure White (PPG Industries, Inc.). Half of the panels were ambient-cured and half of the panels were laser-cured.

[0301] Ambient Cure: The samples were allowed to cure at ambient conditions for 24 hours. The degree of cure was measured using methyl ethyl ketone (MEK) double rubs according to ASTM D5402-19 at 45 minutes cure time and 24 hours cure time. The panels were double rubbed until the coating failed or 100 double rubs were achieved. Results are provided in Table 14 (Samples 1 to 5; acetoacetate hardener), Table 15 (Samples 6 to 10; epoxy-acetoacetate hardener), Table 16 (Samples 11 to 15; acrylate- acetoacetate hardener), and Table 17 (Samples 16 to 20; epoxy-acrylate-acetoacetate hardener).

[0302] Laser Cure: The panels were exposed to the laser at 100°C for 2 minutes with a 30 second ramp. The panels were allowed to cool to room temperature, then degree of cure was measured using MEK double rubs according to ASTM D5402-19. Results are provided in Table 14 (Samples 1 to 5; acetoacetate hardener), Table 15 (Samples 6 to 10; epoxy-acetoacetate hardener), Table 16 (Samples 11 to 15; acrylate-acetoacetate hardener), and Table 17 (Samples 16 to 20; epoxy-acrylate-acetoacetate hardener).Table 14: Samples 1 to 5: Base + Acetoacetate Hardener Results

[0303] The results provided in Table 14 show that laser-cured acetoacetate coatings demonstrated substantially improved cure compared to ambient-cured coatings. All the ambient- cured coatings failed prior to reaching 100 double rubs when measured at 45 minutes postmixing. In contrast, all the laser-cured coatings achieved 100 double rubs immediately following EMR exposure (100°C for 7 minutes plus 30 second ramp). Furthermore, when the coatings were laser-cured, the addition of carbon black (a photothermally active material) to the composition resulted in a substantially lower total energy density required to maintain temperature throughout the cure period compared to compositions containing no photothermally active material. Specifically, Example 6 (Clear), which did not include any carbon black, required 253.77 J / cm2total energy density, while Example 9 (Tinted Clear; 0.011 wt% carbon black on total solids weight) required only 178.92 J / cm2total energy density. Similarly, Example 7 (White), which did not include any carbon black, required an energy density of 465.22 J / cm2, while Example 10 (Tinted White; 0.054 wt% carbon black on total solids weight) demonstrated an energy density requirement of 160.95 J / cm2. Therefore, adding even a small amount of photothermally active carbon black to the compositions resulted in a substantially lower total energy density required to maintain the temperature during laser cure. Example 8 (Black), which contained the highest amount of photothermally active carbon black (4.35% by weight on total solids weight) demonstrated the lowest total energy density of 128.65 J / cm2.Table 15: Base + Epoxy-Acetoacetate Hardener Results

[0304] The results provided in Table 15 show that laser-cured epoxy-acetoacetate coatings demonstrated substantially improved cure compared to the ambient-cured panels. All the ambient-cured coatings failed prior to reaching 100 double rubs when measured at 45 minutes. In contrast, all the laser-cured coatings achieved 100 double rubs immediately following laser exposure. What is more, when the coatings were laser-cured, the addition of carbon black (a photothermally active material) to the composition resulted in a substantially lower total energy density required to maintain temperature throughout the cure period compared to compositions containing no photothermally active material. Specifically, Example 16 (Clear) required 272.45 J / cm2total energy density, while Example 19 (Tinted Clear) required only 176.92 J / cm2total energy density. Similarly, Example 17 (White) required an energy density of 495.28 J / cm2, while Example 20 (Tinted White) demonstrated an energy density requirement of 160.87 J / cm2. Therefore, adding even a small amount of carbon black to the compositions resulted in a substantially lower total energy density required to maintain the temperature during laser cure. Example 18 (Black) demonstrated the lowest total energy density of 128.63 J / cm2.Table 16: Base + Acrylate / Acetoacetate Hardener Results

[0305] The results provided in Table 16 show that laser-cured acrylate-acetoacetate coatings demonstrated substantially improved cure compared to ambient-cured coatings. All the ambient-cured coatings failed prior to reaching 100 double rubs when measured at 45 minutes. In contrast, all the laser-cured coatings achieved 100 double rubs immediately following laser exposure. What is more, when the coatings were laser-cured, the addition of carbon black (a photothermally active material) to the composition resulted in a substantially lower total energy density required to maintain temperature throughout the cure period compared to compositions containing no photothermally active material. Specifically, Example 26 (Clear) required 271.72 J / cm2total energy density, while Example 29 (Tinted Clear) required only 181.38 J / cm2total energy density. Similarly, Example 27 (White) required an energy density of 448.47 J / cm2, while Example 30 (Tinted White) demonstrated an energy density requirement of 163.40 J / cm2. Therefore, adding even a small amount of carbon black to the compositions resulted in a substantially lower total energy density required to maintain the temperature during laser cure. Example 28 (Black) demonstrated the lowest total energy density of 129.78 J / cm2.Table 17: Base + Epoxy / Acrylate / Acetoacetate Hardener Results

[0306] The results provided in Table 17 show that laser-cured epoxy-acrylate- acetoacetate coatings demonstrated substantially improved cure compared to ambient-cured coatings. All the ambient-cured coatings failed prior to reaching 100 double rubs when measured at 45 minutes. In contrast, all the laser-cured coatings achieved 100 double rubs immediately following laser exposure. What is more, when the coatings were laser-cured, the addition of carbon black (a photothermally active material) to the composition resulted in a substantially lower total energy density required to maintain temperature throughout the cure period compared to compositions containing no photothermally active material. Specifically, Example 36 (Clear) required 272.35 J / cm2total energy density, while Example 39 (Tinted Clear) required only 182.47 J / cm2total energy density. Similarly, Example 37 (White) required an energy density of 431.65 J / cm2, while Example 40 (Tinted White) demonstrated an energy density requirement of 159.52 J / cm2. Therefore, adding even a small amount of carbon black to the compositions resulted in a substantially lower total energy density required to maintain the temperature during laser cure. Example 38 (Black) demonstrated the lowest total energy density of 130.06 J / cm2.

[0307] Whereas specific aspects of the disclosure have been described in detail, it will be appreciated by those skilled in the art that various modifications and alternatives to those details could be developed in light of the overall teachings of the disclosure. Accordingly, the particular arrangements disclosed are meant to be illustrative only and not limiting as to the scope of the disclosure which is to be given the full breadth of the claims appended and any and all equivalents thereof.

Claims

We claim:

1. A method of curing a composition, comprising: exposing the composition to electromagnetic radiation (EMR) generated by a defocused laser to cure the composition; wherein the composition comprises (a) an acetoacetate-containing compound and (b) a blocked polyamine.

2. The method of claim 1, wherein the laser is a diode laser.

3. The method of claim 1 or claim 2, wherein the EMR comprises a wavelength of 300 nm to 1,500 nm.

4. The method of any of the preceding claims, wherein the EMR comprises a wavelength of 900 nm to 1,080 nm.

5. The method of any of the preceding claims, wherein the EMR comprises a wavelength of 960 nm to 985 nm.

6. The method of any of the preceding claims, wherein the composition is exposed to the EMR for at least 2 minutes.

7. The method of any of the preceding claims, wherein the composition further comprises a pho to thermally active material.

8. The method of claim 7, wherein the photothermally active material comprises carbon black.

9. The method of claim 7 or claim 8, wherein the composition comprises the photothermally active material in an amount of 0.001 percent by weight to 20 percent by weight based on total solids weight of the composition.

10. The method of any of the preceding claims, wherein the composition further comprises an epoxy-containing compound and / or a (meth)acrylate-containing compound.

11. The method of any of the preceding claims, further comprising applying the composition to a surface of a substrate prior to the exposing.

12. The method of any of the preceding claims, wherein a rate of curing the composition is accelerated compared to a rate of curing the composition not exposed to the EMR.

13. The method of any of the preceding claims, wherein the composition is transparent or reflective.

14. A substrate comprising a coating formed from a composition cured by the method of any of the preceding claims.

15. The substrate of claim 14, wherein the coating has at least 100 methyl ethyl ketone (“MEK”) double rubs performed according to ASTM D5402-19.

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