Methods of curing (METH)acrylate-containing compositions

Abstract

Disclosed are methods of curing a composition comprising (a) a (meth)acrylate-containing compound and (b) an amine-containing compound. 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 (METH)ACRYLATE-CONTAINING COMPOSITIONS CROSS-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 a (meth)acrylate-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) a (meth)acrylate-containing compound and (b) an amine- containing compound.

[0005] Also disclosed are substrates comprising a coating formed from a composition cured by the disclosed methods. BRIEF DESCRIPTION OF THE DRAWINGS

[0006] FIG. 1 is a graph showing the Shore A hardness of cured Example A as a function of time (hours) and cured by laser, oven, or ambient conditions.

[0007] FIG. 2 is a graph showing the Shore A hardness of cured Example B as a function of time (hours) and cured by laser, oven, or ambient conditions.

[0008] FIG. 3 is a graph showing the Shore A hardness of cured Example C as a function of time (hours) and cured by laser, oven, or ambient conditions.

[0009] FIG. 4 is a graph showing the Shore A hardness of cured Example D as a function of time (hours) and cured by laser, oven, or ambient conditions.

[0010] FIG. 5 is a graph showing the Shore A hardness of cured Example E as a function of time (hours) and cured by laser, oven, or ambient conditions.

[0011] FIG. 6 is a graph showing the Shore A hardness of cured Example F as a function of time (hours) and cured by laser, oven, or ambient conditions.

[0012] FIG. 7 is a graph showing the Shore A hardness of cured Example G as a function of time (hours) and cured by laser, oven, or ambient conditions.

[0013] FIG. 8 is a graph showing the Shore A hardness of cured Example H as a function of time (hours) and cured by laser, oven, or ambient conditions.

[0014] FIG. 9 is a graph showing the Shore A hardness of cured Example I as a function of time (hours) and cured by laser, oven, or ambient conditions.

[0015] FIG. 10 is a graph showing the Shore A hardness of cured Example J as a function of time (hours) and cured by laser, oven, or ambient conditions.

[0016] FIG. 11 is a graph showing the Shore A hardness of cured Example K as a function of time (hours) and cured by laser, oven, or ambient conditions. DETAILED DESCRIPTION

[0017] 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.

[0018] As described in more detail below, the composition may comprise (a) a (meth)acrylate-containing compound and (b) an amine-containing compound. Electromagnetic Radiation and Laser

[0019] 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.

[0020] 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.

[0021] 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.

[0022] 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 as 925 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.

[0023] 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% to50%. 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.

[0024] 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.

[0025] The EMR may be monochromatic light from the visible domain to the near- infrared domain. As used herein, the term “monochromatic” refers to light having a narrow bandwidth (+ / - 25 nm) at a nominal wavelength or frequency.

[0026] The EMR may be polychromatic light from the visible domain to the near- infrared domain. As used herein, the term “polychromatic” refers to a light having primarily two or more wavelengths or frequencies.

[0027] 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.

[0028] 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 to result 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.

[0029] 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 thatdoes not diverge or converge over a specified distance, i.e., the beam maintains a substantially constant diameter and direction over a specified distance.

[0030] 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).

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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 µm to 200 µm apart, and connected inparallel 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.

[0037] 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 µm to 600 µm or larger.

[0038] 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.

[0039] 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.

[0040] 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 part thereof, 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 parts 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.

[0041] 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.

[0042] 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 laboratory or industrial settings.

[0043] 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.

[0044] EMR may be generated by a robotically guided laser and / or LED. Photothermally Active Material

[0045] 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= totalzero or start of heating cycle; tmax= time to end of heating cycle, wherein the time from t0 to tmax includes ramp time to a temperature setpoint and hold time at the temperature setpoint (in seconds); %P = the percentage of laser power used in the recorded time interval (as recorded using LASCON Process Manager software by Dr. Mergenthaler GmbH & Co. KG, as part of the controller of the laser system; LP = laser power, 4500 W; Δt = 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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 MxWO3 such as CsWO3; 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.

[0050] The photothermally active material that may be used in the compositions disclosed herein also include calcium carbonate; dolomite; huntite; and / or hydromagnesite.

[0051] 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.

[0052] The photothermally active material that may be used in the compositions disclosed herein also include barium sulfate and / or barium manganate sulfate.

[0053] 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 3,500oC, (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.

[0054] 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 are substantially curved, curled, creased, or buckled. The graphenic carbon nanoparticles may be turbostatic, i.e., adjacent stacked atom layers do not exhibit ordered AB Bernal stacking associated with conventional exfoliated graphene but rather exhibit disordered or non-ABABAB stacking. Alternatively, the graphenic carbon particles may be in the form of nanotubes. The particles typically do not have a spheroidal or equiaxed morphology.

[0055] The photothermally active material that may be used in the compositions disclosed herein also includes cadmium sulfide; cadmium selenide; and / or cadmium sulfoselenide.

[0056] The photothermally active material that may be used in the compositions disclosed herein also include cobalt stannate; cobalt phosphate; and / or cobalt aluminate.

[0057] 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.

[0058] 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.

[0059] The photothermally active material may also include a micronized rubber compound.

[0060] 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.

[0061] The photothermally active material may comprise carbon black, manganese dioxide, and / or copper phthalocyanine such as a solubilized pigment.

[0062] Any combination of the foregoing photothermally active materials disclosed herein above also may be used in the compositions disclosed herein. For example, the photothermally active material may comprise a single photothermal material or may comprise two or more different types of photothermal material.

[0063] The photothermally active material may be soluble or may be in a particulate form.

[0064] 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).

[0065] 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.

[0066] The compositions may comprise the photothermally active material in an amount of at least 0.0001 percent by weight based on total solids weight of the composition, such as at least 0.001 percent by weight, such as at least 0.01 percent by weight, such as at least 1 percent by weight. The compositions may comprise the photothermally active material in an amount of no more than 20 percent by weight based on total solids weight of the composition, such as no more than 15 percent by weight, such as no more than 10 percent by weight. The composition may comprise the photothermally active material in an amount of 0.0001 percent by weight to 20 percent by weight photothermally active material based on total solids weight of the composition, such as 0.001 percent by weight to 15 percent by weight, such as 0.01 percent by weight to 10 percent by weight, such as 1 percent by weight to 10 percent by weight(Meth)acrylate-Containing Compound

[0067] The composition disclosed herein may comprise a (meth)acrylate-containing compound. As used herein, a “(meth)acrylate-containing compound” refers to a compound comprising an acrylate functional group and / or a methacrylate functional group.

[0068] The (meth)acrylate-containing compound may comprise at least 2 olefinic double bonds, such as 2 to 20 olefinic double bonds.

[0069] 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 (meth)acrylate, a polyester (meth)acrylate, a polyether (meth)acrylate, a polyurethane (meth)acrylate, an amino (meth)acrylate, a silicone (meth)acrylate, and / or a melamine (meth)acrylate.

[0070] 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 1,3-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.

[0071] 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 dipentaerythritol 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.

[0072] 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 hydroxyalkyl (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.

[0073] 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.

[0074] The composition may comprise the (meth)acrylate-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 (meth)acrylate-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 (meth)acrylate-containing compound 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. Amine-Containing Compound

[0075] The composition disclosed herein may further comprise an amine-containing compound. The amine-containing compound may be blocked, unblocked, encapsulated, or unencapsulated. Suitable amines for use in the composition disclosed herein can be selected from a wide variety of known amines such as primary amines and / or secondary amines.

[0076] The amine-containing compound may include monoamines or polyamines having at least two functional groups such as di-, tri-, and / or higher functional amines. The amine maybe aromatic and / or aliphatic, such as cycloaliphatic. Non-limiting examples of suitable amines may include aliphatic polyamines such as but not limited to ethylamine, isomeric propylamines, butylamines, pentylamines, hexylamines, cyclohexylamine, ethylene diamine, 1,2- diaminopropane, 1,4-diaminobutane, 1,3-diaminopentane, 1,6-diaminohexane, 2-methyl-1,5- pentane diamine, 2,5-diamino-2,5-dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl-1,6-diamino- hexane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,3- and / or 1,4-cyclohexane diamine, 1- amino-3,3,5-trimethyl-5-aminomethyl-cyclohexane, 2,4- and / or 2,6-hexahydrotoluoylene diamine, 2,4′- and / or 4,4′-diamino-dicyclohexyl methane and 3,3′-dialkyl-4,4′-diamino- dicyclohexyl methanes (such as 3,3′-dimethyl-4,4′-diamino-dicyclohexyl methane and 3,3′- diethyl-4,4′-diamino-dicyclohexyl methane), 2,4- and / or 2,6-diaminotoluene and 2,4′- and / or 4,4′-diaminodiphenyl methane, piperazines or adducts or derivatives thereof, or mixtures thereof.

[0077] Non-limiting examples of suitable secondary amines can include mono- and poly- acrylate and methacrylate modified amines; polyaspartic esters which can include derivatives of compounds such as maleic acid, fumaric acid esters, and / or aliphatic polyamines and the like. The secondary amine may include an aliphatic amine, such as a cycloaliphatic diamine. Such amines are commercially available from Huntsman Corporation (Houston, Tex.) under the designation of JEFFLINK such as JEFFLINK 754 from BASF as Baxxoder PC136.

[0078] The amine-containing compound may comprise an amine-functional resin. Suitable amine-functional resins can be selected from a wide variety known in the art and can include those having a viscosity such as 1 cps to 10,000 cps (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.). The amine- functional resin may be an ester of an organic acid, for example, an aspartic ester-based amine- functional reactive resin that is compatible with isocyanate. The resin may be solvent-free, and / or may have a mole ratio of amine-functionality to the ester of no more than 1:1 so that no excess primary amine remains upon reaction. A non-limiting example of such polyaspartic esters may include the derivative of diethyl maleate and 1,5-diamino-2-methylpentane, which is available commercially from Covestro under the trade name Desmophen NH1220 and the derivative of diethyl maleate and 4,4’-methylenebis (cyclohexan-1-amine), commercially available as Desmophen NH1420 (Covestro). Other suitable compounds containing aspartate groups may be employed as well.

[0079] The amine may include a high molecular weight primary amine, such as but not limited to a polyoxyalkyleneamine. Suitable polyoxyalkyleneamines may contain two or more primary amino groups attached to a backbone derived, for example, from propylene oxide and / or ethylene oxide. Non-limiting examples of such amines may include those available under the designation JEFFAMINE from Huntsman Corporation. Such amines may have a number average molecular weight ranging from 200 g / mol to 7,500 g / mol as reported by the manufacturer, such as but not limited to JEFFAMINE D-230, D-400, D-2000, T-403, T-5000, XJS-616, and ED600. Other suitable amines include aliphatic and cycloaliphatic polyamines such as the Ancamine® series available from Evonik.

[0080] The amine may comprise an alkanolamine. As used herein, the term “alkanolamine” refers to a compound comprising a nitrogen atom bonded to at least one alkanol substituent comprising an alkyl group comprising a primary, secondary or tertiary hydroxyl group. The alkanolamine may have the general structure R1nN(R2-OH)3-n, wherein R1comprises hydrogen or an alkyl group, R2comprises an alkanediyl group, and n = 0, 1 or 2. When n = 2, two R1groups will be present, and these groups may be the same or different. When n = 0 or 1, 2 or 3 R2-OH groups will be present, and these groups may be the same or different. The alkyl groups comprise aliphatic linear or branched carbon chains that may be unsubstituted or substituted with, for example, ether groups. Suitable alkanolamines include monoalkanolamines such as ethanolamine, N-methylethanolamine, 1-amino-2-propanol, and the like, dialkanolamines such as diethanolamine, diisopropanolamine, and the like, and trialkanolamines such as trimethanolamine, triethanolamine, tripropanolamine, tributanolamine, tripentanolamine, trihexanolamine, triisopropanolamine, and the like.

[0081] The composition may comprise the amine 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 amine 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 amine 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.Accelerator

[0082] The compositions 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.

[0083] 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.

[0084] 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 paragraphs

[0098] through

[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-31J, Ajicure PN-40J, Ajicure MY-24 and Ajicure MY-2, all available from Ajinomoto Fine-Techno Co., Inc.

[0085] 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-N,N-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).

[0086] 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.

[0087] 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”), 1,8-diazabicylo[5.4.0]undec-7-ene (“DBU”), 1,5- diazabicyclo[4.3.0]non-5-ene (“DBN”), and / or 1,5,7-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).

[0088] 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 0.1% 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 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 0.1% by weight to 5% by weight.Additives, Fillers, and Solvent

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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 total solids weight of the composition, such as no more than 10% by weight, such as no more than 5% by weight. Additive(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.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] The composition can include a solvent, such as an organic solvent and / or water. As used herein, the term “organic solvent” refers to carbon-based substances capable of dissolving or dispersing other substances.

[0098] 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.

[0099] 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% by weight 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. Compositions

[0100] 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.

[0101] 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.

[0102] The composition may be substantially free, essentially free, or completely free of a photopolymerizable initiator.

[0103] 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.

[0104] The composition may be formulated as a one-component composition, a two- component composition, or a higher-component composition.

[0105] As used herein, a “1K” or “one-component” composition is a composition in which all the ingredients may be premixed and stored at ambient conditions and wherein the reactive 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.

[0106] 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.

[0107] The compositions disclosed herein may be formulated as a 1K composition comprising, consisting essentially of, or consisting of (i) a (meth)acrylate-containing compoundand (ii) an amine-containing compound, and (iii) optionally a photothermally active material, an accelerator, an additive, a solvent, and / or a filler.

[0108] 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 a (meth)acrylate-containing compound; and a second component comprising, consisting essentially of, or consisting of an amine-containing compound. The first component and / or the second component may optionally 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.

[0109] 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

[0110] Disclosed herein are methods of curing any of the compositions described above.

[0111] 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.

[0112] 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.

[0113] 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.

[0114] The methods may comprise exposing the composition to EMR for at least 7 minutes.

[0115] The methods may comprise exposing the compositions comprising the (meth)acrylate-containing compound and the amine-containing compound to EMR with a ramp from ambient to a temperature setpoint of at least 60oC and then held at the temperature setpoint of at least 60oC for at least 7 minutes to cure the composition.

[0116] 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 as no 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.

[0117] 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.

[0118] 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.

[0119] 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 adhesionpromoter, 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.

[0120] 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.

[0121] 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.

[0122] 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 second substrates. 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.

[0123] 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.

[0124] 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.

[0125] The methods disclosed herein may be performed using a robotically guided laser and / or LED.

[0126] The methods disclosed herein may include “flashing” or a “dwell time” prior to exposing the compositions to EMR, such as to remove volatile components from the composition, such as solvents including organic solvents and / or water, or to allow for flow and leveling. The flash or dwell time may be at ambient or elevated temperature. In methods that include an elevated temperature flash step or dwell time, the heating of the applied composition may be from conventional means such as a convection oven or from exposure to EMR. As usedherein, “flashing” refers to exposing the composition to conditions under which solvents begin to evaporate. As used herein, “dwell time” refers to an amount of time a composition is in contact with a substrate surface prior to further processing or drying.

[0127] 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.

[0128] 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.

[0129] 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 the components 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

[0130] The methods disclosed herein may comprise a dual cure method wherein the composition is exposed to EMR to achieve a Shore A hardness and thereafter the composition may continue to cure through dark cure. The compositions disclosed herein may achieve a ShoreA hardness following the onset of exposing the composition to the EMR, while the composition may dark cure under ambient conditions to achieve increased physical properties, such as Shore A hardness, at least 1 hour following termination of the exposure to EMR, such as at least 3 hours, such as at least 24 hours, such as at least 48 hours, such as at least 192 hours.

[0131] The methods disclosed herein may cure a composition to form a coating and may accelerate cure, while maintaining the performance achieved by coatings formed from the compositions cured at ambient conditions. For example, exposure of the compositions disclosed herein to EMR generated by a laser and / or an LED may cure the composition following exposure to the EMR for a 30 second ramp from ambient to at least 60oC and held at such temperature for at least 7 minutes. This is demonstrated, for example, by the increase in Shore A hardness measured according to ASTM D2240-15 at least 20 minutes following exposure to the EMR.

[0132] It was surprisingly and unexpectedly discovered that exposure of the compositions disclosed herein to EMR generated by a laser and / or an LED resulted in sufficient heat generation to initiate cure of the composition. It was surprisingly and unexpectedly discovered that the compositions disclosed herein comprising a photothermally active material required a reduced total energy density to cure the composition. 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.

[0133] It was surprisingly discovered that 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 cure the composition upon exposure to the EMR (i) held at a temperature setpoint of at least 60°C for at least 7 minutes. Such methods may result in a coating having similar or improved mechanical properties, such as hardness, compared to compositions cured under conventional electric oven conditions.

[0134] It was surprisingly and unexpectedly discovered that 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 60oC for at least 7 minutes of less than 350 J / cm2, such as less than 325 J / cm2, such as less than 300 J / cm2, such as less than 275 J / cm2, such as less than 250J / cm2, such as less than 200 J / cm2. It was also surprisingly and unexpectedly discovered the total energy density required to ramp and maintain a composition disclosed herein comprising a photothermally active material at a temperature setpoint of 60oC for at least 7 minutes was reduced by at least 5%, such as by at least 10%, such as by at least 15%, such as by at least 20%, such as by at least 25%, such as by at least 30%, 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 7 minutes.

[0135] It was surprisingly and unexpectedly discovered that 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, at a temperature setpoint of 60oC for at least 7 minutes, may result in a coating achieving a Shore A hardness, measured 20 minutes following termination of the exposure to the EMR and according to ASTM D2240-15, of at least 20. The methods disclosed herein also may result in a coating having a Shore A hardness, measured 1 hour following the exposure to the EMR and according to ASTM D2240-15 of at least 40, such as at least 60. The methods disclosed herein also may result in a coating having a Shore A hardness, measured 3 hours following the exposure to the EMR and according to ASTM D2240-15 of at least 55, such as at least 70. The methods disclosed herein also may result in a coating having a Shore A hardness, measured 24 hours following the exposure to the EMR and according to ASTM D2240-15 of at least 70, such as at least 75. The methods disclosed herein also may result in a coating having a Shore A hardness, measured 48 hours following the exposure to the EMR and according to ASTM D2240-15 of at least 70, such as at least 80. The methods disclosed herein also may result in a coating having a Shore A hardness, measured 192 hours following the exposure to the EMR and according to ASTM D2240-15 of at least 75, such as at least 85.

[0136] 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 dark cure or 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, maintained dark cure mechanisms, and an adhesively robust coating. As used herein, “cure on demand” refers to a composition whose cure rate and / or degree of cure, as measured byShore A hardness as a function of time, for example, can be accelerated by exposure of the composition to EMR having a wavelength of 900 nm to 1,080 nm, such as 960 nm to 985 nm, as disclosed herein. Substrates

[0137] 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 electronic components 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.

[0138] “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.

[0139] 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.

[0140] 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 EV31A 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.

[0141] 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.

[0142] 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

[0143] 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.

[0144] 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.

[0145] 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.

[0146] 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.

[0147] 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.

[0148] 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.

[0149] 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.

[0150] As used herein, a “sealant composition” refers to a composition that forms a sealant in its cured state.

[0151] 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.

[0152] As used herein, a “gap filler composition” refers to a composition that forms a gap filler in its cured state.

[0153] 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.

[0154] As used herein, an “adhesive composition” refers to a composition that forms an adhesive in its cured state.

[0155] As used herein, an “adhesive” refers to a coating that produces a load-bearing joint.

[0156] As used herein, a “pottant composition” refers to a composition that, when cured, forms a pottant.

[0157] As used herein, a “pottant” refers to an encapsulant.

[0158] As used herein, a “pre-preg” refers to a composition pre-impregnating reinforcement fibers prior to cure.

[0159] As used herein, a “liquid shim composition” refers to a composition that, when cured, forms a liquid shim.

[0160] As used herein, a “liquid shim” refers to a coating that eliminates gaps between substrate surfaces.

[0161] 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 10oC to 40oC 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).

[0162] 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.

[0163] 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 composition begins 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.

[0164] 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 / 1D).

[0165] 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, —CONH2refers to an amide functional group that is bonded to another chemical moiety through the carbon atom.

[0166] 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.

[0167] 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 substituentbeing 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.

[0168] 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.

[0169] In view of the foregoing description the present disclosure thus relates in particular to the following Aspects 1 to 113 without being limited thereto.

[0170] 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) a (meth)acrylate-containing compound and (b) an amine-containing compound.

[0171] Aspect 2. 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) a(meth)acrylate-containing compound and (b) an amine-containing compound.

[0172] Aspect 3. The method of aspect 1 or aspect 2, wherein the EMR comprises visible light and / or near infrared light.

[0173] 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.

[0174] Aspect 5. The method of any of the preceding aspects, wherein the EMR comprises a wavelength of at least 960 nm.

[0175] 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.

[0176] 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.

[0177] 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.

[0178] 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.

[0179] Aspect 10. The method of any of the preceding aspects, wherein the EMR comprises a wavelength of 960 nm to 985 nm.

[0180] 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.

[0181] Aspect 12. The method of any of the preceding aspects, wherein the EMR is directional.

[0182] Aspect 13. The method of any of the preceding aspects, wherein the EMR comprises monochromatic light and / or polychromatic light.

[0183] Aspect 14. The method of any of the preceding aspects, wherein the EMR is coherent.

[0184] Aspect 15. The method of any of aspects 1 and 3 to 14, wherein the laser and / or the LED is defocused.

[0185] Aspect 16. The method of any of the preceding aspects, wherein the laser generates diffuse EMR, divergent EMR, and / or collimated EMR.

[0186] 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.

[0187] 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.

[0188] 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.

[0189] 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.

[0190] 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.

[0191] Aspect 22. The method of any of the preceding aspects, wherein the laser has a wall plug efficiency of 60 percent to 80 percent.

[0192] 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.

[0193] 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.

[0194] 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.

[0195] Aspect 26. The method of aspect 24, wherein the temperature sensor controls a temperature of the composition, a temperature of a substrate, and / or a ramp rate.

[0196] 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.

[0197] 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.

[0198] 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.

[0199] Aspect 30. The method of any of the preceding aspects, wherein the composition further comprises a photothermally active material.

[0200] Aspect 31. The method of aspect 30, wherein the photothermally active material comprises carbon black, copper phthalocyanine, and / or manganese dioxide.

[0201] Aspect 32. The method of aspect 30 or aspect 31, wherein the composition comprises the photothermally active material in an amount of at least 0.0001 percent by weight based on total solids weight of the composition, such as at least 0.001 percent by weight.

[0202] Aspect 33. The method of any of aspects 30 to 32, wherein the composition comprises the photothermally active material in an amount of at least 0.01 percent by weight based on total solids weight of the composition, such as at least 1 percent by weight.

[0203] Aspect 34. The method of any of aspects 30 to 33, wherein the composition comprises the photothermally active material in an amount of no more than 20 percent by weight based on total solids weight of the composition, such as no more than 15 percent by weight.

[0204] Aspect 35. The method of any of aspects 30 to 33, 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.

[0205] Aspect 36. The method of any of aspects 30 to 32 and 34, wherein the composition comprises the photothermally active material in an amount of 0.0001 percent by weight to 20 percent by weight based on total solids weight of the composition, such as 0.001 percent by weight to 15 percent by weight.

[0206] Aspect 37. The method of any of aspects 30 to 33, 35, and 36 wherein the composition comprises the photothermally active material in an amount of 0.01 percent by weight to 10 percent by weight based on total solids weight of the composition, such as 1 percent by weight to 10 percent by weight.

[0207] Aspect 38. The method of any of the preceding aspects, wherein the (meth)acrylate-containing compound comprises at least 2 olefinic double bonds, such as 2 to 20 olefinic double bonds.

[0208] Aspect 39. The method of any of the preceding aspects, wherein the (meth)acrylate-containing compound comprises a di(meth)acrylate, a tri(meth)acrylate, and / or a tetra(meth)acrylate.

[0209] Aspect 40. The method of any of the preceding aspects, wherein the (meth)acrylate-containing compound comprises a (meth)acrylic-functional copolymer, an epoxy resin (meth)acrylate, a polyester (meth)acrylate, a polyether (meth)acrylate, a polyurethane (meth)acrylate, an amino (meth)acrylate, a silicone (meth)acrylate, and / or a melamine (meth)acrylate.

[0210] Aspect 41. The method of any of the preceding aspects, wherein the composition comprises the (meth)acrylate-containing compound in an amount of at least 1percent by weight based on total solids weight of the composition, such as at least 3 percent by weight.

[0211] Aspect 42. The method of any of the preceding aspects, wherein the composition comprises the (meth)acrylate-containing compound in an amount of at least 5 percent by weight based on total solids weight of the composition.

[0212] Aspect 43. The method of any of the preceding aspects, wherein the composition comprises the (meth)acrylate-containing compound in an amount of no more than 95 percent by weight based on total solids weight of the composition, such as no more than 90 percent by weight.

[0213] Aspect 44. The method of any of the preceding aspects, wherein the composition comprises the (meth)acrylate-containing compound in an amount of no more than 85 percent by weight based on total solids weight of the composition.

[0214] Aspect 45. The method of any of the preceding aspects, wherein the composition comprises the (meth)acrylate-containing compound in an amount of 1 percent by weight to 95 percent by weight based on total solids weight of the composition, such as 3 percent by weight to 90 percent by weight.

[0215] Aspect 46. The method of any of the preceding aspects, wherein the composition comprises the (meth)acrylate-containing compound in an amount of 5 percent by weight to 85 percent by weight based on total solids weight of the composition.

[0216] Aspect 47. The method of any of the preceding aspects, wherein the amine- containing compound is blocked or unblocked.

[0217] Aspect 48. The method of any of aspects 1 to 46, wherein the amine-containing compound is encapsulated or unencapsulated.

[0218] Aspect 49. The method of any of the preceding aspects, wherein the amine- containing compound comprises a primary amine and / or a secondary amine.

[0219] Aspect 50. The method of any of the preceding aspects, wherein the amine- containing compound comprises a monoamine or a polyamine.

[0220] Aspect 51. The method of any of the preceding aspects, wherein the amine- containing compound comprises an aromatic amine and / or an aliphatic amine, such as a cycloaliphatic amine.

[0221] Aspect 52. The method of any of the preceding aspects, wherein the composition comprises the amine-containing compound in an amount of at least 1 percent by weight based on total solids weight of the composition, such as at least 3 percent by weight.

[0222] Aspect 53. The method of any of the preceding aspects, wherein the composition comprises the amine-containing compound in an amount of at least 5 percent by weight based on total solids weight of the composition.

[0223] Aspect 54. The method of any of the preceding aspects, wherein the composition comprises the amine-containing compound in an amount of no more than 95 percent by weight based on total solids weight of the composition, such as no more than 90 percent by weight.

[0224] Aspect 55. The method of any of the preceding aspects, wherein the composition comprises the amine-containing compound in an amount of no more than 85 percent by weight based on total solids weight of the composition.

[0225] Aspect 56. The method of any of aspects 1 to 55, wherein the composition comprises the amine-containing compound in an amount of 1 percent by weight to 95 percent by weight based on total solids weight of the composition, such as 3 percent by weight to 90 percent by weight.

[0226] Aspect 57. The method of any of the preceding aspects, wherein the composition comprises the amine-containing compound in an amount of 5 percent by weight to 85 percent by weight based on total solids weight of the composition.

[0227] Aspect 58. The method of any of the preceding aspects, wherein the composition further comprises an accelerator.

[0228] Aspect 59. The method of aspect 58, wherein the composition comprises the accelerator in an amount of at least 0.001 percent by weight based on total solids weight of the composition, such as at least 0.1 percent by weight.

[0229] Aspect 60. The method of aspect 58 or aspect 59, wherein the composition comprises the accelerator in an amount of no more than 10 percent by weight based on total solids weight of the composition, such as no more than 5 percent by weight.

[0230] Aspect 61. The method of any of aspects 58 to 60, wherein the composition comprises the accelerator in an amount of 0.001 percent by weight to 10 percent by weight based on total solids weight of the composition, such as 0.1 percent by weight to 5 percent by weight.

[0231] Aspect 62. The method of any of the preceding aspects, wherein the composition further comprises an additive, a filler, and / or a solvent.

[0232] Aspect 63. The method of aspect 62, 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.

[0233] Aspect 64. The method of aspect 62 or aspect 63, wherein the composition comprises the additive in an amount of at least 0.01 percent by weight based on total solids weight of the composition, such as at least 0.1 percent by weight.

[0234] Aspect 65. The method of any of aspects 62 to 64, wherein the composition comprises the additive in an amount of no more than 15 percent by weight based on total solids weight of the composition, such as no more than 5 percent by weight.

[0235] Aspect 66. The method of any of aspects 62 to 65, wherein the composition comprises the additive in an amount of 0.01 percent by weight to 15 percent by weight based on total solids weight of the composition, such as 0.1 percent by weight to 5 percent by weight.

[0236] Aspect 67. The method of any of aspects 62 to 66, wherein the composition comprises the filler in an amount of at least 0.1 percent by weight based on total solids weight of the composition, such as at least 1 percent by weight.

[0237] Aspect 68. The method of any of aspects 62 to 67, wherein the composition comprises the filler in an amount of no more than 90 percent by weight based on total solids weight of the composition, such as no more than 80 percent by weight.

[0238] Aspect 69. The method of any of aspects 62 to 68, wherein the solvent comprises water.

[0239] Aspect 70. The method of any of aspects 62 to 68, wherein the solvent comprises an organic solvent.

[0240] Aspect 71. The method of any of aspects 62 to 70, wherein the composition comprises the solvent in an amount of at least 5 percent by weight based on total weight of the composition, such as at least 20 percent by weight.

[0241] Aspect 72. The method of any of aspects 62 to 71, wherein the composition comprises the solvent in an amount of no more than 80 percent by weight based on total weight of the composition, such as no more than 60 percent by weight.

[0242] Aspect 73. The method of any of aspects 62 to 72, wherein the composition comprises the solvent in an amount of 5 percent by weight to 80 percent by weight based on total weight of the composition, such as 20 percent by weight to 60 percent by weight.

[0243] Aspect 74. The method of any of the preceding aspects, wherein the composition has a total solids content of at least 20 percent by weight based on total weight of the composition, such as at least 40 percent by weight.

[0244] Aspect 75. The method of any of the preceding aspects, wherein the composition has a total solids content of at least 60 percent by weight, such as at least 80 percent by weight.

[0245] Aspect 76. The method of any of the preceding aspects, wherein the composition has a total solids content of 100 percent by weight based on total weight of the composition.

[0246] Aspect 77. The method of any of the preceding aspects, wherein the composition is substantially free, essentially free, or completely free of a photopolymerizable initiator.

[0247] Aspect 78. 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.

[0248] Aspect 79. The method of any of the preceding aspects, wherein the composition is formulated as a 1K composition, a 2K composition, and / or a higher-component composition.

[0249] Aspect 80. The method of any of aspects 26 to 79, comprising applying the composition to a surface of the substrate, such as by extruding, pressing, grouting, caulking, spreading, brushing, rolling, troweling, dipping, and / or spraying.

[0250] Aspect 81. The method of any of the preceding aspects, wherein the composition is exposed to the EMR for at least 7 minutes.

[0251] Aspect 82. 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.

[0252] Aspect 83. 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.

[0253] 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 108W / cm2, such as no more than 106W / cm2.

[0254] Aspect 85. 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.

[0255] Aspect 86. 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.

[0256] Aspect 87. 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.

[0257] Aspect 88. The method of any of aspects 1 to 83 and 85, 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.

[0258] Aspect 89. The method of any of aspects 1 to 83 and 86 to 88, 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.

[0259] Aspect 90. The method of any of aspects 80 to 89, comprising cleaning and / or deoxidizing the substrate surface.

[0260] Aspect 91. The method of any of aspects 80 to 90, comprising coating the substrate surface with a coating composition in addition to the composition, such as a pretreatment composition, an electrodepositable coating composition, a primer coating composition, a basecoat coating composition, and / or a topcoat coating composition.

[0261] Aspect 92. The method of any of aspects the preceding aspects, wherein the substrate comprises a fixed structure.

[0262] Aspect 93. The method of any of aspects 80 to 92, comprising applying the composition to a damaged portion of the surface of the substrate.

[0263] Aspect 94. The method of any of aspects 80 to 93, wherein the surface comprises a pre-existing coating, and wherein the pre-existing coating is at least partially removed prior to the applying.

[0264] Aspect 95. The method of any of aspects 80 to 94, wherein a temperature of the surface of the substrate does not exceed 121oC upon exposure to the EMR.

[0265] Aspect 96. The method of any of aspects 80 to 95, 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.

[0266] Aspect 97. The method of any of the preceding aspects, further comprising flashing the composition prior to the exposure to the EMR.

[0267] Aspect 98. The method of any of the preceding aspects, wherein a total energy density of less than 350 J / cm2is required to cure the coating, such as less than 325 J / cm2.

[0268] Aspect 99. The method of any of the preceding aspects, wherein a total energy density of less than 300 J / cm2is required to cure the coating, such as less than 275 J / cm2.

[0269] Aspect 100. The method of any of the preceding aspects, wherein a total energy density of less than 250 J / cm2is required to cure the coating, such as less than 200 J / cm2.

[0270] 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 5% 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 10%.

[0271] 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 15% 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 20%.

[0272] Aspect 103. The method of any of aspects 30 to 102, 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%.

[0273] Aspect 104. The method of any of aspects 30 to 103, wherein a total energy density required to cure the composition was reduced by at least 40% compared to a total energy density required to cure a composition that did not comprise the photothermally active material.

[0274] Aspect 105. The method of any of aspects 26 to 105, wherein a temperature of the substrate following exposure to the EMR is below a heat deflection temperature of the substrate.

[0275] Aspect 106. A substrate comprising a coating formed from the composition cured by the method of any of the preceding aspects.

[0276] Aspect 107. The substrate of aspect 119, wherein the coating comprises a sealant, an adhesive, a gap filler, a pottant, a prepreg, and / or a liquid shim.

[0277] Aspect 108. The substrate of aspect 106 or aspect 107, wherein the coating has a Shore A hardness of at least 20; wherein the Shore A hardness is measured 20 minutes of the exposure to the EMR and according to ASTM D2240-15.

[0278] Aspect 109. The substrate of any of aspects 106 to 108, wherein the coating has a Shore A hardness of at least 40, such as at least 60; wherein the Shore A hardness is measured 1 hour of the exposure to the EMR and according to ASTM D2240-15.

[0279] Aspect 110. The substrate of any of aspects 106 to 109, wherein the coating has a Shore A hardness of at least 55, such as at least 70; wherein the Shore A hardness is measured 3 hours of the exposure to the EMR and according to ASTM D2240-15.

[0280] Aspect 111. The substrate of any of aspects 106 to 110, wherein the coating has a Shore A hardness of at least 70, such as at least 75; wherein the Shore A hardness is measured 24 hours of the exposure to the EMR and according to ASTM D2240-15.

[0281] Aspect 112. The substrate of any of aspects 106 to 111, wherein the coating has a Shore A hardness of at least 70, such as at least 80; wherein the Shore A hardness is measured 48 hours of the exposure to the EMR and according to ASTM D2240-15.

[0282] Aspect 113. The substrate of any of aspects 106 to 112, wherein the coating has a Shore A hardness of at least 75, such as at least 80; wherein the Shore A hardness is measured 192 hours of the exposure to the EMR and according to ASTM D2240-15.

[0283] Illustrating the disclosure are the following examples, which, however, are not to be considered as limiting the disclosure to their details. EXAMPLES

[0284] For all laser-exposed samples, the laser unit used was a Compact Heating and Drying SYS-CD system supplied by IPG Photonics®Corporation (Marlborough, MA) outfittedwith a Class I laser, laser wavelength of 960 nm to 985 nm (model number DLS-4500-U-ECO) projected onto a 20cm x 20cm area using an enclosure (model number SYSMACDHE000004U).ax5.0.0.32 8 9 6 E C 90.8.5 n 1 21 210.0 04.o 0 italu5.0.0.32 8 0 5 mrB 90.3.4 o 1 21 210.0 10.0 F e ni5.0.0.3 8 5 4 m A 92.0.30 A- 1 21 21 0 0.10.5 0 etalrr k-T -)l y Teg(S6)lcerae1c e en5 mIe gme)lAnekc0)ani2)ni3) i44)U)uetaMTul(:dama06g(P30g(00g(ma5g(Bg(icn dB )”rehtvit aicreBrr l tm mceia 14 1soa r aa aNaKoPtDa n M Ataf feybl f f sC o CrM m“A H(h B Pe eb aAJ Ja cp(T.1ciMm e6e c50hna4.1.1Cymr0tlofaireceP 54 0.11.pe0Svi0 ntonewim 5 3M.o .M5 1 10.4 3 mproro m fCGor6elnaA f50.b mseel4.1 0 1alb iastirv ntsala u uiad v 5ylHnI a4 0.11.0lamy0ico ki llarrfn.eeoiclrcbvenIm malEm,r10.mmol1ocia,voroo ea f ct, Calylell en b ne-ne11.y 0racicalia7-Pa rcev m iaa cmedort nf1 h moylplcai u]elb 10.0ila,e cr 0.4.alil ni emm5[ aav n molae )lsglakl c)laoide)sdoitareocyycle e()me)lalg(me)ltaTsrail cn ht,tilbainadi ”2reviaiB ) reviaiP. b(osue syaz creg xOhttcretn”Bhttcrexi t lnaoialfayllaaim dnotaaob Cota tam wir atxo oep tad- mey yo o m mr%t hocMB“ 8 / t,a (h h AaM n“(A3,1 CC AAp p( (o m 1 2 4 5 6

[0285] The individual formulations were prepared and mixed using a Hauschild Speedmix DAC mixer, model 600.1 FVZ. The formulations consisted of two parts, the Base Pack and the Hardener Pack. The Base Pack was prepared by combining all the listed Base Pack components in Table 1, in the listed order. The materials were mixed using the DAC mixer for 2 minutes at 2200 rpm. The mixture was inspected and mixed manually with a spatula to ensure homogeneity. The Hardener Pack was prepared by weighing out the single component in the amount set forth in Table 1 for each formulation.

[0286] The Base and Hardener Packs were manually mixed together in the ratios listed in Table 1, then cast into aluminum weigh pans for all hardness testing. Cure of the samples was monitored for 8 days using Shore A hardness durometer measurements according to ASTM D2240-15.

[0287] Laser exposed samples. The samples in aluminum weigh pans were exposed to the laser at 60°C for 7 minutes with a 30 second ramp. Shore A hardness was measured according to ASTM D2240-15 at the times indicated in Table 2.

[0288] Oven exposed samples. The samples in aluminum weigh pans were placed in an oven at 60°C for 7 minutes. Shore A hardness was measured according to ASTM D2240-15 at the times indicated in Table 3.

[0289] Ambient-cured samples. Samples were kept in an environment-controlled cabinet at 25°C, 50% relative humidity (Thermofisher Forma #3940), then Shore A hardness was measured after 27 minutes (to match laser and oven exposure times plus cooling time). Shore A hardness was then measured at the times indicated in Table 4.lerusopxEresaLtsoPselpmax G % 1.B 0 53 742119 E 0C 67 77enimA- 2etF %O 1 7 3 n 0 5 507970858alM yrc7A 4f2o%O 7 14440elE 1 n 0 3 5 6 7 7 8ifMorPeru D %2 1.On 0 04 27159 C 0 55 77 7sMsendraBHCA0 1 9 % 6 566174797A1erohS:B % 1.B 0 26 4657220A 66778elbaT % A 1 0B . 8 83 A 0 4 56475708 0 s el ,-epru -etrni r r r s smer sosousom h h h yayaa P p x P p021 34 x 2d2dEexe8

[0290] Table 2 provides the Shore A hardness measurements of the laser-cured samples of Examples A to K at the listed time intervals. As demonstrated, all the samples demonstrated cure 20 minutes post-EMR exposure. 24 hours following EMR exposure, all samples had a Shore A hardness of at least 71. The samples continued to cure, with Shore A hardnesses between 76 and 85 recorded 8 days following EMR exposure. Examples D to F demonstrated that as the concentration of MnO2increased, the Shore A hardness increased at all measurement times.l Tairo)Ken tPsdyl0 7 3205961737lxE.Ce0nimA- 2etF %O 3 n 0 08 2868781929aly Mrc9A 4f2oE %On 0 3 94645el1 6 6 7 7 88ifMorPer2 u D % 1.On 0 52 349029 C 0 5777sMsendraB 6 9HCA0 % 2 335962767A1erohS:B % 1 B 0 2 450073.0A 2 457 77elbaT % A 1 0B 0 51 232546564 A 7.0 s eler ,p - -erne ustsus i r r s shrhh yayarmom oo 4d d13 P p 0a p P 2282xx xe eE

[0291] Table 3 provides the Shore A hardness measurements of the oven-cured samples of Examples A to K at the listed time intervals. As shown, all but Examples E and F demonstrated significantly lower cure 20 minutes post-oven exposure compared to the laser- cured samples, indicating that laser-curing provides accelerated cure of the compositions. Additionally, the laser-cured samples of all but Examples E and F demonstrated comparable or improved Shore A hardness compared to the oven-cured samples.lorT,lPa)t itKnreosyl0 0312889iiielp G % 1.B 0 0614576070ma0C 7 x Eeni2 m F %O 5455 3 n 0 0A- 3 6 7 708etMal1y 5rc2 AfE %O 1 n 0 0 825669617oMelifor2PeD % 1.On 0 011548r0 66627 u M CsseB nd 86rCA0 0a% 3 5468617H1Aeroh B % 1.B 0 027890 S 0A 2 4 6 6 7:4elbaT % A 1 0B . 0 0911547072 A 7 0 s el-er .pu ni r r r s smer sa om h h h y4aydaP p x 71 3 xe2 2 2d8 E

[0292] Table 4 provides the Shore A hardness measurements of the ambient-cured samples of Examples A to K at the listed time intervals. As shown, the ambient-cured samples demonstrated no cure at 27 minutes after being placed in the environment-controlled cabinet, compared to laser-cured samples, which, as discussed above, provided an accelerated cure. All the ambient-cured samples demonstrated lower final Shore A hardness at 8 days compared to the laser-cured samples.lortT,la)itKnP roseyl10elp HC7m% 2a1 x Eeni% m.B 0 G1C 6 0 1A-etaly 2rcF %O 9 3 n 7 AfM 1 oa3ta5 2DytE %O 1 1 n 9isM 1neDy 2 greD% 1.O 1 n 2 n 0 M 1 E:5elBb A8aC 1 T % 2 1 B% 1.B 5 A 7 0 1 % A1 B 9 0.0 A 81 s etlply atgar ytC2)m oe °niax Tsm ne06c / EJE D(

[0293] Table 5 shows the energy density data during laser cure. 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 of 60oC for 7 minutes 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.

[0294] 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

1. 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) a (meth)acrylate-containing compound and (b) an amine-containing compound.

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 7 minutes.

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

8. The method of claim 7, wherein the photothermally active material comprises carbon black, MnO2, and / or copper phthalocyananine.

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, further comprising dark-curing the composition following the exposure to the EMR.

11. The method of any of the preceding claims, wherein a total energy density of less than 350 J / cm2is required to cure the coating.

12. The method of any of claims 7 to 11, wherein the total energy density required to cure the composition was reduced by at least 5% compared to a total energy density required to cure a composition that did not comprise the photothermally active material.

13. The method of any of the preceding claims, wherein the laser is a mobile device, a hand- held device, and / or a robotically guided device.

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

15. The method of claim 14, further comprising cleaning, deoxidizing, abrading, and / or pretreating the surface of the substrate prior to the applying.

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

17. The substrate of claim 16, wherein the coating: (a) a Shore A hardness of at least 20, measured at least 20 minutes following termination of the exposure to the EMR; (b) a Shore A hardness of at least 40, measured at least 1 hour following termination of the exposure to the EMR; (c) a Shore A hardness of at least 55, measured at least 3 hours following termination of the exposure to the EMR;(d) a Shore A hardness of at least 70, measured at least 24 hours following termination of the exposure to the EMR; (e) a Shore A hardness of at least 70 measured at least 48 hours following termination of the exposure to the EMR; and / or (f) a Shore A hardness of at least 75 measured at least 192 hours following termination of the exposure to the EMR;. wherein the Shore A hardness is measured according to ASTM D2240-15.

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