Methods of curing isocyanate-containing compositions

Abstract

Disclosed are methods of curing a composition. The method includes exposing the composition to electromagnetic radiation generated by a laser for a period of time sufficient to cure the composition. The composition may include an isocyanate-containing compound and an active hydrogen-containing compound. Also disclosed are substrates comprising a coating formed from a coating cured by any of the methods disclosed herein.

Description

METHODS OF CURING ISOCYANATE-CONTAINING COMPOSITIONSCROSS-REFERENCE TO RELATED APPLICATIONS

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

[0002] Methods of curing a composition containing an isocyanate-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 herein 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 an isocyanate-containing compound and an active hydrogencontaining compound.

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

[0006] FIG. 1 is a graph showing the Shore A hairiness of Example 13 as a function of time (days) and cured by laser, oven, or ambient conditions.

[0007] FIG. 2 is a graph showing the Shore A hairiness of Example 14 as a function of time (days) and cured by laser, oven, or ambient conditions.

[0008] FIG. 3 is a graph showing the Shore A hardness of Example 15 as a function of time (days) and cured by laser, oven, or ambient conditions.

[0009] FIG. 4 is a graph showing the Shore A hairiness of Example 16 as a function of time (days) and cured by laser, oven, or ambient conditions.

[0010] FIG. 5 is a graph showing the Shore A hardness of Example 17 as a function of time (days) and cured by laser, oven, or ambient conditions.

[0011] FIG. 6 is a graph showing the Shore A hardness of Example 18 as a function of time (days) and cured by laser, oven, or ambient conditions.

[0012] FIG. 7 is a graph showing the Shore A hardness of Example 19 as a function of time (days) and cured by laser, oven, or ambient conditions.

[0013] FIG. 8 is a graph showing the Shore A hardness of Example 20 as a function of time (days) and cured by laser, oven, or ambient conditions.DETAILED DESCRIPTION

[0014] 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.

[0015] As described in more detail below, the composition may comprise an isocyanate- containing compound and an active hydrogen-containing compound.Electromagnetic Radiation and Laser

[0016] 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.

[0017] 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.

[0018] 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.

[0019] 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.

[0020] The EMR may be generated as a continuous wave, a quasi-continuous wave, and / or a pulsed wave. As used herein, “continuous wave,” when used with respect to EMR, refers to a constant, uninterrupted beam of light as long as the laser is powered and having a duty cycle of 100%. As used herein, “quasi-continuous wave,” when used with respect to EMR, refers to a series of pulses of light beams with intervals of no emission and having a duty cycle of greater than 50% to less than 100%. As used herein, “pulsed wave,” when used with respect to EMR, refers to a series of pulses of light beams with a duration of femtoseconds to milliseconds separated by intervals of no emission and having a duty cycle of greater than 0% to 50%. As used herein, “duty cycle” refers to the percentage of time that light is actively emitted by laser during a given period of operation. Duty cycle may be calculated according to the following formula: Duty Cycle (D) = (Pulse Duration) / (Pulse Period) * 100%, where “pulse duration” is the time interval during which the laser emits light in one pulse, wherein “pulse period” is the total time interval of one cycle including the pulse duration plus the off time (when the laser is not emitting light). The person skilled in the art of laser technologies will understandthat the selection of duty cycle impacts thermal management and power output and must he compatible with the cure chemistry and the substrate to which the composition is applied.

[0021] 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.

[0022] The EMR may be monochromatic light from the visible domain to the nearinfrared domain. As used herein, the term “monochromatic” refers to light having a narrow bandwidth (+ / - 25 nm) at a nominal wavelength or frequency.

[0023] The EMR may be polychromatic light from the visible domain to the nearinfrared domain. As used herein, the term “polychromatic” refers to a light having primarily two or more wavelengths or frequencies.

[0024] 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.

[0025] 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.

[0026] The laser may generate EMR that is diffuse, divergent, and / or collimated. As used herein, “diffuse,” when used with respect to EMR, refers to light that is scattered by molecules, particles, or surfaces before reaching its destination. As used herein, “divergent,” when used with respect to EMR, refers to a light beam that spreads out or expands as it propagates away from the light source. The diameter of a divergent EMR light beam increases with distance from the source. As used herein, “collimated,” when used with respect to EMR, refers to a plurality of light rays that are parallel or substantially parallel, resulting in a beam that does not diverge or converge over a specified distance, i.e., the beam maintains a substantially constant diameter and direction over a specified distance.

[0027] 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).

[0028] 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.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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 mm to 200 mm apart, and connected in parallel or in series. As used herein, a “diode laser stack” refers to an assembly of multiple diode laser bars stacked vertically or arranged in arrays. A diode laser stack may comprise, for example, 5 or more diode laser bars, such as up to 20 diodes, such as up to 300 diodes, such as more than 300 diodes.

[0034] 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 permanently connected to an optical fiber, forming a single unit. Fibers may comprise multi-mode fibers with core diameters of, for example, 100 mm to 600 mm or larger.

[0035] 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.

[0036] 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.

[0037] 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.

[0038] 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.

[0039] 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.

[0040] 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.

[0041] EMR may be generated by a robotically guided laser and / or LED.Photothermally Active Material

[0042] 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: t Z-max %P x LpAX AtoEquation 1, where Etot = total energy density in J / cm2; to = time zero or start of heating cycle;= time to end of heating cycle, wherein the time from to to tmaxincludes 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; At = 0.02 seconds between recorded data points, ; and A = the projection area of the laser output, 400 cm2. As used herein, “temperature setpoint” refers to a preset temperature to which the coating is ramped and at which the coating is maintained over the heating cycle. Temperature setpoint may be measured using an infrared thermometer or similar device to measure the temperature of the coating. Temperatures from the infrared thermometer may be read by the controller described above to adjust the EMR generated by the laser system over the heating cycle to ramp or maintain the coating temperature at the temperature setpoint.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] The photothermally active material that may be used in the compositions disclosed herein also include lime; iron oxide such as hematite, magnetite and siderite; chromium oxide; hydrated chromium oxide; chromium trioxide; antimony trioxide; antimony pentoxide; antimony tin oxide; indium tin oxide; cerium oxide; titanium dioxide, such as rutile and anatase titanium dioxide; tungsten oxide; doped tungsten oxides having the formula MxWCh such as CsWCh; reduced tungsten oxide such as violet tungsten oxide; tungstate; tungsten bronzes; vanadium oxide; cupric carbonate hydroxide; copper hydroxide; layered double hydroxide such as hydrotalcite; titanium nitride; and / or organic quaterrylene.

[0047] The photothermally active material that may be used in the compositions disclosed herein also include calcium carbonate; dolomite; huntite; and / or hydromagnesite.

[0048] 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.

[0049] The photothermally active material that may be used in the compositions disclosed herein also include barium sulfate and / or barium manganate sulfate.

[0050] The photothermally active material that may be used in the compositions disclosed herein also include carbon black; graphite; graphene; and / or graphenic carbonparticles. Graphene may be a thermal graphene such as turbostatic thermal graphene. Graphene may be in the form of commercially available nanoparticlcs such as exfoliated graphite. Graphenic carbon particles (i) may be thermally produced from a hydrocarbon precursor material capable of forming a two-carbon-fragment species or a hydrocarbon material comprising methane introduced into a thermal zone at a temperature of greater than 3,500°C, (ii) may have an average aspect ratio of greater than 3:1, (iii) may have a BET specific surface area of greater than 70 m2 / g, and / or (iv) may have a Raman spectroscopy 2D / G peak ratio of at least 0.9:1. Graphenic carbon particles may be produced by methods such as those disclosed in U.S. Patent No. 8,486,363 and U.S. Patent No. 8,486,364, each incorporated herein by reference in its entirety.

[0051] 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- AB AB AB stacking. Alternatively, the graphenic carbon particles may be in the form of nanotubes. The particles typically do not have a spheroidal or equiaxed morphology.

[0052] The photothermally active material that may be used in the compositions disclosed herein also includes cadmium sulfide; cadmium selenide; and / or cadmium sulfoselenide.

[0053] The photothermally active material that may be used in the compositions disclosed herein also include cobalt stannate; cobalt phosphate; and / or cobalt aluminate.

[0054] 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.

[0055] 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.

[0056] The photothermally active material may also include a micronized rubber compound.

[0057] 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.

[0058] The photothermally active material may comprise carbon black, manganese dioxide, copper phthalocyanine such as a solubilized pigment, and / or silicon carbide.

[0059] 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.

[0060] The photothermally active material may be soluble or may be in a particulate form.

[0061] 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, suchas 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).

[0062] 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.

[0063] 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.Isocyanate-Containing Compounds

[0064] The compositions disclosed herein may comprise an isocyanate-containing compound. As used herein, “isocyanate-containing compound” refers to a compound comprising one or more isocyanate functional groups (-N=C=O). The isocyanate-containingcompound may be monofunctional (“monoisocyanate”) and / or polyfunctional (“polyisocyanatc”). The isocyanate-containing compound may comprise a monomer, a small molecule, a polymer, and / or a prepolymer.

[0065] The isocyanate may comprise an unblocked isocyanate and / or a blocked isocyanate. As used herein, a “blocked isocyanate” refers to an isocyanate wherein a portion of the isocyanate functional group(s) is blocked by a blocking group introduced by reaction of an isocyanate functional group with a blocking agent. As used herein, “blocked” means that the isocyanate functional group has been reacted with a blocking agent such that the resultant blocked isocyanate functional group is stable to active hydrogens at ambient temperature but reactive with active hydrogens when heated. As used herein, a “blocking agent” refers to a compound comprising a functional group reactive with an isocyanate functional group, so that when reacted the isocyanate functional group is blocked by a blocking group derived from the functional group, resulting in a blocked isocyanate. As used herein, an “unblocked isocyanate” refers to an isocyanate in which the isocyanate functional group(s) are not blocked by a blocking group.

[0066] Suitable monoisocyanates include p-tolyl isocyanate, hexyl isocyanate, phenyl isocyanate, isocyanate ethyl acrylate, methacryloyloxyethyl isocyanate, and / or 3- (triethyoxysilyl)propyl isocyanate.

[0067] Suitable polyisocyanates include C2-C20 linear, branched, cyclic, aliphatic and / or aromatic polyisocyanates.

[0068] Suitable isocyanate prepolymers include a reaction product of a polyisocyanate and a polyol.

[0069] Aliphatic polyisocyanates may include (i) alkylene isocyanates, such as trimethylene diisocyanate; tetramethylene diisocyanate, such as 1 ,4-tetramethylene diisocyanate; pentamethylene diisocyanate, such as 1,5 -pentamethylene diisocyanate and 2-methyl-l,5- pentamethylene diisocyanate; hexamethylene diisocyanate (“HDI”), commercially available as Demodur XP 2617 (Covestro), such as 1 ,6-hexamethylene diisocyanate and / or 2,2,4- and 2,4,4- trimethylhexamethylene diisocyanate; heptamethylene diisocyanate, such as 1,7-heptamethylene diisocyanate; propylene diisocyanate, such as 1,2-propylene diisocyanate; butylene diisocyanate, such as 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, and / or 1,4-butylene diisocyanate; ethylene diisocyanate; decamethylene diisocyanate, such as 1,10-decamethylene diisocyanate; ethylidene diisocyanate; and butylidene diisocyanate. Aliphatic polyisocyanatcs may also include (ii) cycloalkylcnc isocyanates, such as: cyclopcntanc diisocyanate, such as 1,3-cyclopentane diisocyanate; cyclohexane diisocyanate, such as 1,4- cyclohexane diisocyanate, 1,2-cyclohexane diisocyanate, isophorone diisocyanate (“IPDI”), methylene bis(4-cyclohexylisocyanate) (“HMDI”); and mixed aralkyl diisocyanates such as tetramethylxylyl diisocyanates, such as meta- tetramethylxylylene diisocyanate (commercially available as TMXDI® from Allnex SA). Dimers, trimers, oligomers, and / or polymers of the above-mentioned polyisocyanates also may be used such as the cyclotrimer of 1,6 hexamethylene diisocyanate (also known as the isocyanate trimer of HDI, commercially available as Desmodur N3300® (Covestro AG)).

[0070] Aromatic polyisocyanates may include arylene isocyanates, such as phenylene diisocyanate, such as m-phenylene diisocyanate, p-phenylene diisocyanate, and / or chlorophenylene 2,4-diisocyanate; and / or naphthalene diisocyanate, such as 1,5 -naphthalene diisocyanate and / or 1,4-naphthalene diisocyanate. Aromatic polyisocyanates may also include alkarylene isocyanates, such as: methylene-interrupted aromatic diisocyanates, such as 4,4'- diphenylene methane diisocyanate (“MDI”), and alkylated analogs such as 3,3'-dimethyl-4,4'- diphenylmethane diisocyanate, and polymeric methylenediphenyl diisocyanate; toluene diisocyanate (“TDI”), such as 2,4-tolylene, 2,6-tolylene diisocyanate, and / or bitoluene diisocyanate; and 4,4-toluidine diisocyanate; xylene diisocyanate; dianisidine diisocyanate; xylylene diisocyanate; and / or other alkylated benzene diisocyanates.

[0071] The polyisocyanates may comprise triisocyanates, such as triphenyl methane- 4,4',4''-triisocyanate, 1,3,5-triisocyanato benzene, and 2,4,6-triisocyanato toluene; tetraisocyanates, such as 4,4'-diphenyldimethyl methane-2,2',5,5'-tetraisocyanate; and polymerized polyisocyanates, such as tolylene diisocyanate dimers and trimers and the like. The blocked isocyanate may comprise a polymeric polyisocyanate, such as polymeric HDI, polymeric MDI, polymeric isophorone diisocyanate, and the like. The blocked isocyanate may also comprise a blocked trimer of hexamethylene diisocyanate, commercially available as Desmodur N33OO® from Covestro AG.

[0072] The isocyanate compound may comprise a functional group in addition to the isocyanate functional group(s).

[0073] The composition may comprise the isocyanate-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, such as at least 5 percent by weight. The composition may comprise the isocyanate-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, such as no more than 85 percent by weight. The composition may comprise the isocyanate-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, such as 5 percent by weight to 85 percent by weight.Active Hydrogen-Containing Compounds

[0074] The composition may comprise an active hydrogen-containing compound. As used herein, an “active hydrogen-containing compound” refers to a compound containing an active hydrogen. As used herein, an “active hydrogen” refers to a hydrogen that can be displaced when reacting with the isocyanate-containing compound and can be determined, for example, by the Zerewitinoff test. The active hydrogen-containing compound may be blocked, unblocked, encapsulated, or encapsulated. The active hydrogen-containing compound may comprise a hydroxyl-containing compound, an amine, and / or a thiol.

[0075] The active hydrogen-containing compound may comprise a hydroxyl-containing compound. The hydroxyl-containing compound may be monomeric and / or polymeric.Examples of hydroxyl-containing compounds include polyols, such as diols, triols, and higher hydric alcohols, such as ethylene glycol; propylene glycol; 1,2-butanediol; 1,4-butanediol; 1,3- butanediol; 2,2,4-trimethyl-l,3-pentanediol; 1,5-pentanediol; 2,4-pentanediol; 1,6-hexanediol; 2,5-hexanediol; 2-methyl-l,3-pentanediol; 2-methyl-2,4-pentanediol; 2,4-heptanediol; 1,6- hexanediol; 2,5-hexanediol; 2-methyl-l,3-pentanediol; 2-methyl-2, 4, -pentanediol; 2,4- heptanediol; 2-ethy 1-1, 3 -hexanediol; 2,2-dimethyl-l,3-propanediol; 1,4-cyclohexanediol; 1,4- cyclohexanedimethanol; l,2-bis(hydroxymethyl)cyclohexane; 1,2- bis(hydroxyethyl)cyclohexane; 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3- hydroxypropionate; diethylene glycol; dipropylene glycol; bis hydroxypropyl hydantoins; tris hydroxyethyl isocyanurate; monoethanolamine; diethanolamine; triethanolamine; N-methyl- monoethanolamine; 2-hydroxymethyl-2-dimethylamino- 1 ,3-propanediol; 2-hydroxymethyl-2- dimethylamino- 1 -propanol; and the like.

[0076] Non-limiting examples of suitable polymeric polyols include (meth)acrylic polyols, polyester polyols, polyether polyols, polycaprolactone polyols, polycarbonate polyols, polyurethane polyols, polymers containing hydroxy functional acrylates and / or methacrylates, polymers containing allyl alcohols, hydroxyl functional butadienes, amide-containing polyols, polyhydric polyvinyl alcohols, cellulose and derivatives thereof, and / or urethane polyols. As used herein, “(meth)acrylic” refers to both acrylics and methacrylates.

[0077] Examples of suitable polyether polyols may include polyether diols such as Terathane® 200, Terathane® 650, Terathane® PTMEG250, and Terathane® PTMEG 650, all commercially available from Invista ,the PolyTHF® and Pluracol® polyether diols, all commercially available from BASF, Pripol™ diols or Priplast™ polyols, all commercially available from Cargill, polycaprolactone-based polyols such as those those sold under the trade name Capa™, such as Capa 2054, Capa 2077A, Capa 2085, Capa 2205, Capa 3031, Capa 3050, Capa 3091 and / or Capa 4101, all commercially available from Perstorp Group. In addition, polyols based on dimer diols sold under the trade name Solvermol™, commercially available from BASF, or bio-based polyols, such as the tetrafunctional polyol Agrol 4.0, commercially available from BioBased Technologies, may also be utilized. Examples of suitable hydroxylcontaining compounds are disclosed in U.S. Patent No. 4,798,745, 3:50 to 6:63, the cited portions of which are incorporated herein by reference.

[0078] The active hydrogen-containing compound may comprise an amine-containing compound. 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.

[0079] The amine may include monoamines, or polyamines having at least two functional groups such as di-, tri-, and / or higher functional amines. The amine may be aromatic and / or aliphatic, such as cycloaliphatic. Non-limiting examples of suitable amines may include aliphatic poly amines 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-l ,5-pentane diamine, 2,5- diamino-2,5-dimethylhexane, 2,2,4- and / or 2,4, -trimethyl- 1 ,6-diamino-hexane, 1,11- diaminoundecane, 1,12-diaminododecane, 1,3- and / or 1,4-cyclohexane diamine, l-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- dicyclohcxyl methane), 2,4- and / or 2,6-diaminotolucnc and 2,4'- and / or 4,4'-diaminodiphcnyl methane, piperazines or adducts or derivatives thereof, or mixtures thereof.

[0080] Non-limiting examples of suitable secondary amines can include mono- and polyacrylate 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 available commercially from Huntsman Corporation (Houston, Tex.) under the designation of JEFFLINK such as JEFFLINK 754 from BASF as Baxxoder PC136.

[0081] The amine 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 relatively low 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 isocyanate may be solvent-free, and / or has 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 l,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.

[0082] The amine may include a high molecular weight primary amine, such as but not limited to poly oxy alkyleneamine. 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 JEFF AMINE 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 JEFF AMINE 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.

[0083] 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-u, 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, A-methylethanolamine, l-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.

[0084] The active hydrogen-containing compound may comprise a thiol-containing compound. The thiol may comprise a monothiol compound and / or a polythiol compound. As used herein, a “monothiol compound” refers to a chemical compound having one thiol functional group (-SH) per molecule and a “polythiol compound” refers to a chemical compound having more than one thiol functional groups (-SH) per molecule.

[0085] The thiol may comprise any polymer having thiol functionality, such as a thiol- functional polyether (also referred to herein as a “poly thioether”), a thiol-functional polyurethane, and the like.

[0086] The monothiol compound may include t-dodecane thiol, n-dodecyl mercaptan, p- toluenethiol, quinoline thiol, 1 -thioglycerol, mercaptosuccinic acid, thiosalicylic acid, 2- aminoethanethiol, and / or 2-thiocytosine.

[0087] The polythiol compound comprises a compound comprising more than one thiol functional groups. The polythiol compound may comprise a dithiol, trithiol, tetrathiol, pentathiol, hexathiol, and / or higher functional polythiol compound. As used herein, a “dithiol” refers to a compound comprising more than one to two thiol functional groups. The polythiol compound may comprise a dithiol compound, such as 3,6-dioxa-l,8-octanedithiol (DMDO), 3- oxa-l,5-pentanedithiol, 1 ,2-ethanedithiol, 1,3-propanedithiol, 1 ,2-propanedithiol, 1,4- butanedithiol, 1,3-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,3-pentanedithiol, 1,6-hexanedithiol, 1 ,3-dithio-3-methylbutane, ethylcyclohexyldithiol (ECHDT), mcthylcyclohcxyldithiol, mcthyl-substitutcd dimcrcaptodicthyl sulfide, dimcthyl-substitutcd dimercaptodiethyl sulfide, 2,3-dimercapto-l -propanol, bis-(4-mercaptomethylphenyl) ether, 2,2'- thiodiethanethiol, and / or glycol dimercaptoacetate (commercially available as THIOCURE® GDMA from BRUNO BOCK Chemische Fabrik GmbH & Co. KG). As used herein, “trithiol” refers to a compound comprising more than two to three thiol functional groups. The poly thiol compound may comprise a trithiol compound such as trimethylolpropane trimercaptoacetate (commercially available as THIOCURE® TMPMA from BRUNO BOCK Chemische Fabrik GmbH & Co. KG), trimethylopropane tris-3-mercaptopropionate (commercially available as THIOCURE® TMPMP from BRUNO BOCK Chemische Fabrik GmbH & Co. KG), ethoxylated trimethylpropane tri(3-mercaptopropionate) polymer (commercially available as THIOCURE® ETTMP from BRUNO BOCK Chemische Fabrik GmbH & Co. KG), and / or tris[2-(3- mercaptopropionyloxy)ethyl]isocyanurate (commercially available as THIOCURE® TEMPIC from BRUNO BOCK Chemische Fabrik GmbH & Co. KG). As used herein, “tetrathiol” refers to a compound comprising more than three to four thiol functional groups. The polythiol compound may comprise a tetrathiol compound such as pentaerythritol tetramercaptoacetate (commercially available as THIOCURE® PETMA from BRUNO BOCK Chemische Fabrik GmbH & Co. KG), pentaerythritol tetra-3-mercaptopropionate (commercially available as THIOCURE® PETMP from BRUNO BOCK Chemische Fabrik GmbH & Co. KG), and / or polycaprolactone tetra(3-mercaptopropionate) (commercially available as THIOCURE® PCL4MP 1350 from BRUNO BOCK Chemische Fabrik GmbH & Co. KG). Higher functional polythiol compounds may include dipentaerythritol hexa-3-mercaptopropionate (commercially available as THIOCURE® DiPETMP from BRUNO BOCK Chemische Fabrik GmbH & Co. KG). Combinations of thiols may also be used.

[0088] A polythioether useful in the compositions of the present disclosure may have the structure of formula (I):HS— R1— [— S— (CH2)P— O— (— R2— O— )m— (CH2)q— S— R1— ]n— SH (I) wherein R1denotes a C2-10 n-alkanediyl, C2-6 branched alkylene, Ce-s cycloalkylene, or Ce- 10 alkylcycloalkylene group, heterocyclic, — [( — CHi)p — X]q— ( — CHi)r; or — [( — CHi)P— X]q— ( — CH2)I — in which at least one — CH2 — unit is substituted with a methyl group; R2denotes a C2-10 n-alkylene, C2-6 branched alkylene, Ce-8 cycloalkylene, or Ce-14 alkylcycloalkylene group,heterocyclic, — [( — CH2)P— X]q— ( — CH2)r; each X is independently selected from the group consisting of O, S, S-S, and — NR6— ; R6denotes H or methyl; m is an independently selected rational number from 1 to 50; and n is an independently selected integer from 1 to 60; p is an independently selected integer from 2 to 6; q is an independently selected integer from 1 to 5; and r is an independently selected integer from 2 to 10. In an example of the foregoing polymer, R1is C2-C6 alkyl and R2is C2-C6 alkyl.

[0089] Poly thioethers according to the present disclosure may have the formula (II):B— {R8CH2CH2— O— (R2— O)mCH2CH2— S— R1— [— S— CH2CH2— O— (R2— O)m— CH2— S— R1],!— SH}z orB— {R8— S— R1— [— S— CH2CH2— O— (R2— O)m— CH2— S— R^n— SH}z wherein B denotes a z-valent residue of a polyfunctionalizing agent, R1, R2, n, and m denote structures and values discussed above with reference to Formula I, R8denotes a residue of a terminal vinyl group or thiol group, and z is an integer from 3 to 6.

[0090] Other suitable polythioethers for use in the compositions of the present disclosure include, for example, mercapto-propionates, mercapto-acetates, and / or mercapto-acrylates.

[0091] Examples of suitable mercapto-propionates for use in the compositions of the present disclosure include pentaerythritol tetra(3-mercapto-propionate) (PETMP), trimethylolpropane tri(3-mercaptopropionate) (TMPMP), glycol di(3-mercaptopropionate) (GDMP), tris[2- (3-mercapto-propionyloxy)ethyl]isocyanurate (TEMPIC), di-pentaerythritol hexa(3- mercaptopropionate) (di-PETMP), tri(3-mercaptopropionate) pentaerythritol, and / or triethylolethane tri-(3-mercaptopropionate) .

[0092] Examples of suitable polymeric thiols for use in the compositions of the present disclosure include ethoxylated trimethylolpropane tri(3-mercaptopropionate), and / or polycaprolactone tetra-3-mercaptopropionate.

[0093] Examples of suitable mercapto-acetates for use in the compositions of the present disclosure include pentaerythritol tetramercaptoacetate (PRTMA), trimethylolpropane trimercaptoacetate (TMPMA), glycol dimercaptoacetate (GDMA), ethyleneglycol dimercaptoacetate, and / or di-trimethylolpropane tetramercaptoacetate.

[0094] The polythiol compound may have a thiol equivalent weight of at least 80 g / eq, such as at least 100 g / eq, such as at least 125 g / eq, such as at least 400 g / eq, and may have a thiolequivalent weight of no more than 4,000 g / eq, such as no more than 2,500 g / eq, such as no more than 2,000 g / cq, such as no more than 1,650 g / cq. The polythiol compound may have a thiol equivalent weight of 80 g / eq to 4,000 g / eq, such as 100 g / eq to 2,500 g / eq, such as 125 g / eq to 2,000 g / eq, such as 400 g / eq to 1,650 g / eq. As used herein, “thiol equivalent weight” is determined by dividing the measured Mw of a thiol-containing compound by the average number of thiol functional groups present in the thiol-containing compound.

[0095] The composition may comprise the active hydrogen-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, such as at least 5 percent by weight. The composition may comprise the active hydrogen-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, such as no more than 85 percent by weight. The composition may comprise the active hydrogencontaining 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, such as 5 percent by weight to 85 percent by weight.Accelerator

[0096] The compositions disclosed herein optionally may comprise an accelerator in addition to the isocyanate-containing compound and the active hydrogen-containing compound. The accelerator may comprise a catalyst. The catalyst may comprise a latent catalyst, such as a blocked catalyst or an encapsulated catalyst.

[0097] The catalyst may comprise an amine catalyst and / or nitrogen-based catalyst. The catalyst may comprise a tertiary amine, such as a cyclic tertiary amine, a quaternary amine, an N- heterocyclic carbene, and / or an amidine / guanidine. Suitable catalysts that may be used in the present disclosure include N, A-dimcthylcyclohcxylaminc, A,A-dimethylethanolamine, A-methyl morpholine, 2,2’ -dimorpholinodiethylether, dimethylaminoethoxyethanol, triethylenediamine, triethylamine, tetramethylguanidine, bis(2-dimethylaminoethyl)ether, N,N,N’- trimethylaminoethylethanolamine, N,N,N ’,N ’-tetramethyl- 1 ,6-hexanediamine, 1,3,5- tris(dimethylaminopropyl)-hexahydro-s-triazine, 1 ,8-diazabicyclo[5.4.0]undec-7-ene, A-(3- aminopropyl)imidazole, 1,2-dimethylimidazole, l,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,4- diazabicyclo[2.2.2]octane (“DABCO”), l,8-diazabicylo[5.4.0]undec-7-ene (“DBU”), 1,5- diazabicyclo[4.3.0]non-5-ene (“DBN”), and / or 7-methyl-l,5,7-triazabicyclo[4.4.0]dec-5-ene.

[0098] Suitable cyclic tertiary amines include l,4-diazabicyclo[2.2.2]octane (“DABCO”), l,8-diazabicylo[5.4.0]undec-7-ene (“DBU”), l,5-diazabicyclo[4.3.0]non-5-ene (“DBN”), and / or l,5,7-triazabicyclo[4.4.0]dec-5-ene (“TBD”). Examples of suitable quaternary amines include tetrabutylammonium bromide, tetrabutylammonium chloride, and / or benzyltrimethylammonium bromide.

[0099] In some cases, the catalyst may comprise an organic acid, such as diphenyl phosphate, methanesulfonic acid, and / or triflic acid.

[0100] The catalyst may comprise an organometallic complex. Suitable organometallic complexes include titanates, such as tetrabutyl titanate or tetrapropyl titanate, tin compounds, such as dibutyltin dilaurate, dibutyltin diacetate, tin octoate, or dibutyl tin oxide, or other metal compounds, such as chelates of bismuth, zinc, zirconium, titanium, aluminum, and / or iron, such as zirconium acetylacetonate and / or iron acetylacetonate.

[0101] The catalyst may comprise a Lewis Acid catalyst. Examples of suitable Lewis acid catalysts 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).

[0102] The composition may comprise 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 0.01 percent by weight, such as at least 0.1 percent by weight. The composition may comprise 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 8 percent by weight, such as no more than 5 percent by weight. The composition may comprise 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 0.01 percent by weight to 8 percent by weight, such as 0.01 percent by weight to 5 percent by weight, such as 0.1 percent by weight to 5 percent by weight.Additives, Fillers, and Solvents

[0103] The composition disclosed herein optionally may comprise an additive in amounts known to those skilled in the art. 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.

[0104] As used herein, the term “reactive diluent” refers to a molecule or a compound that would not be considered a volatile organic compound and 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 and / or composition.

[0105] As used herein, the term “non-reactive diluent” refers to a molecule or a compound that would not be considered a volatile organic compound and 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 and / or composition.

[0106] 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.

[0107] Additive(s), if present at all, may be present in the composition in a combined amount of at least 0.01 percent by weight based on total solids weight of the composition, such as at least 0.05 percent by weight, such as at least 0.1 percent by weight. Additive(s), if present at all, may be present in the composition in a combined 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. Additive(s), if present at all, may be present in the composition in an amount of 0.01 percent by weight to 20 percent by weight based on total solids weight of the composition, such as 0.05 percent by weight to 15 percent by weight, such as 0.1 percent by weight to 10 percent by weight.

[0108] The compositions 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.

[0109] The composition may comprise the filler(s), if present at all, in a combined amount of at least 0.1 percent by weight based on total weight of the composition, such as at least 1 percent by weight. The composition may comprise the filer(s), if present at all, in a combined amount of no more than 30 percent by weight based on total weight of the composition, such as no more than 20 percent by weight. The composition may comprise thefiller(s), if present at all, in a combined amount of 0.1 percent by weight to 30 percent by weight based on total weight of the composition, such as at least 1 percent by weight to 20 percent by weight.

[0110] The compositions disclosed herein optionally may comprise a solvent. As used herein, “solvent” refers to a substance capable of dissolving or dispersing other substances at ambient conditions.

[0111] The solvent may comprise 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. Suitable organic solvents include esters, such as alkyl acetates, such as ethyl acetate, n-butyl acetate, and / or n-hexyl acetate; ketones, such as methyl ethyl ketone and / or methyl isobutyl ketone; glycol ethers; alcohols; and / or hydrocarbons, such as toluene, xylene, aromatic hydrocarbons, and / or aliphatic hydrocarbons such as hexane, heptane, and / or nonane.

[0112] The composition may comprise solvent in an amount of at least 1 percent by weight based on total weight of the composition, such as at least 5 percent by weight, such as at least 10 percent by weight, such as at least 20 percent by weight, such as at least 30 percent by weight. The composition may comprise solvent in an amount of no more than 90 percent by weight based on total weight of the composition, such as no more than 85 percent by weight, such as no more than 80 percent by weight, such as no more than 70 percent by weight, such as no more than 60 percent by weight. The composition may comprise solvent in an amount of 1 percent by weight to 90 percent by weight based on total weight of the composition, such as 5 percent by weight to 85 percent by weight, such as 10 percent by weight to 80 percent by weight, such as by 20 percent by weight to 70 percent by weight, such as 30 percent by weight to 60 percent by weight.Compositions

[0113] 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.

[0114] The composition may have a total solids content of at least 10 percent by weight based on total weight of the composition, such as at least 20 percent by weight, such as at least 30 percent by weight, such as at least 40 percent by weight, such as at least 50 percent by weight, such as at least 60 percent by weight, such as at least 70 percent by weight, such as at least 80percent by weight, such as at least 99 percent by weight, and may have a total solids content of 100 percent by weight based on total weight of the composition. The composition may have a total solids content of 10 percent by weight to 100 percent by weight based on total weight of the composition, such as 20 percent by weight to 100 percent by weight, such as 30 percent by weight to 100 percent by weight such as 40 percent by weight to 100 percent by weight, such as 50 percent by weight to 100 percent by weight, such as 60 percent by weight to 100 percent by weight, such as 70 percent by weight to 100 percent by weight, such as 80 percent by weight to 100 percent by weight, such as 90 percent by weight to 100 percent by weight.

[0115] The composition may be substantially free, essentially free, or completely free of a photopolymerizable initiator.

[0116] 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.

[0117] The composition may be formulated as a one-component composition, a two- component composition, or a higher-component composition, such as a three-component composition.

[0118] As used herein, a “IK” or “one-component” composition, is a composition in which all the ingredients may be premixed and stored at ambient conditions and wherein the reactive components do not readily react at ambient or slightly thermal conditions such as greater than ambient temperature and less than 60°C. One-component compositions may cure upon exposure to EMR and / or may react at an accelerated rate upon exposure to EMR compared to a cure rate in the absence of EMR. In the absence of such exposure, the composition will remain largely uncured.

[0119] The compositions disclosed herein may be formulated as a I K composition comprising, consisting essentially of, or consisting of an isocyanate-containing compound and an active hydrogen-containing compound and optionally a photothermally active material, an accelerator, an additive, a filler, and / or a solvent.

[0120] 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 thatthe two components of the composition are stored separately from each other and mixed just prior to application of the composition. Two-componcnt compositions may be exposed to EMR as described herein. As used herein, “reactive components” refer to components of the final composition containing the isocyanate-containing compound and the active hydrogen-containing compound.

[0121] The compositions disclosed herein may be formulated as a 2K composition comprising, consisting essentially of, or consisting of: a first component comprising, consisting essentially of, or consisting of an isocyanate-containing compound; and a second component comprising, consisting essentially of, or consisting of an active hydrogen-containing compound. The first component and / or the second component may further comprise a photothermally active material, an accelerator, an additive, a filler, and / or a solvent, so long as such ingredients do not react with other ingredients in the component under ambient conditions. The first and second components may be mixed immediately prior to use.

[0122] 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

[0123] The compositions 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 a EMR generated by a laser and / or an LED as described above. The composition can be applied to the surface of a substrate in any number of different ways by depositing, applying, or contacting the composition to a substate surface to form a coating thereon, non-limiting examples of which include extruding, pressing, grouting, caulking, spreading, brushing, rolling, troweling, dipping, spraying including airless spraying, high volume low pressure systems, electrostatic systems, coil coating, spin coating, and the like. Optionally, the substrate may be attached to a moveable mount or stage.

[0124] Compositions may be applied in different environments such as a spray booth, a hangar, a paint shop, or a clean room based on 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. Coating repair or application may take place in remote locations lacking booths, hangars, or portable enclosures.

[0125] 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.

[0126] 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 Shore A 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.

[0127] 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.

[0128] The methods may comprise exposing the compositions comprising the isocyanate-containing compound and the active hydrogen-containing compound to EMR with a ramp from ambient to a temperature setpoint of at least 60°C and then held at the temperaturesetpoint of at least 60°C for at least 10 minutes to cure the composition. The methods may comprise exposing the compositions comprising the isocyanate-containing compound and the active hydrogen-containing compound to EMR with a ramp from ambient to a temperature setpoint of at least 100°C and then held at the temperature setpoint of at least 100°C for at least 5 minutes, such as at least 15 minutes to cure the composition. The methods may comprise exposing the compositions comprising the isocyanate-containing compound and the active hydrogen-containing compound to EMR with a ramp from ambient to a temperature setpoint of at least 140°C and then held at the temperature setpoint of at least 140°C for at least 15 minutes to cure the composition.

[0129] 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 10 W / cm“, such as no more than 10 W / cm , such as no more than 10 W / cm , 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.

[0130] 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, a liquid shim, an article, and / or a part.

[0131] 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.

[0132] The methods disclosed herein may further comprise coating the substrate surface with a coating composition in addition to the composition disclosed herein. That is, the methods may further comprise treating the substrate surface with a pretreatment composition and / or coating the substrate surface with an electrodepositable coating composition, a primer coating composition, a basecoat coating composition, a topcoat coating composition, an adhesion promoter, and the like, as understood by those skilled in the art of substrate protection. That is,“contacting a surface of the substrate” encompasses contacting a surface of a substrate that has been treated with other coatings, as described herein.

[0133] 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.

[0134] 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.

[0135] 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.

[0136] 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.

[0137] 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.

[0138] The methods disclosed herein may be performed using a robotically guided laser and / or LED.

[0139] The methods disclosed herein may include “flash” 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 conditions. 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 used herein, “flashing” refers to exposing the composition to conditions under whichsolvents 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.

[0140] 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.

[0141] It was surprisingly and unexpectedly discovered that exposure of the compositions comprising the photothermally active material disclosed herein to EMR generated by a laser and / or an LED resulted in sufficient heat generation by the photothermally active material 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.

[0142] 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 100°C for at least 5 minutes; (ii) held at a temperature setpoint of at least 60°C for at least 10 minutes; and / or (iii) held at a temperature setpoint of at least 100°C, such as at least 140°C, for at least 15 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.

[0143] It was surprisingly and unexpectedly discovered that exposure of a waterborne 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 andmaintain the composition at a temperature of 100°C for at least 5 minutes of less than 700 J / cm2, such as less than 475 J / cm2, such as less than 375 J / cm2, such as less than 325 J / cm2, such as less than 300 J / cm2. It was also surprisingly and unexpectedly discovered the total energy density required to ramp and maintain a waterborne compositions disclosed herein comprising a photothermally active material at a temperature setpoint of 100°C for at least 5 minutes was reduced by at least 25%, such as by at least 30%, such as by at least 35%, such as by at least 40% compared to total energy density required to ramp and maintain the same composition that did not include a photothermally active material at the temperature setpoint for at least 5 minutes. It was surprisingly and unexpectedly discovered that exposure of a waterborne 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 100°C for at least 5 minutes, (i) may result in a coating having a Konig hardness, measured after the coating cooled to ambient temperature and at least 20 minutes following the exposure to the EMR and according to ASTM D4366, of at least 149, such as at least 165, such as at least 170, such as at least 175, such as at least 180, and / or (ii) may result in a coating achieving 100 MEK double rubs, measured after the coating cooled to ambient temperature and at least 30 minutes following the exposure to the EMR and according to ASTM D5402-19.

[0144] It also was surprisingly discovered that exposure of a 100% solids 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 held at a temperature setpoint of at least 60°C for at least 10 minutes and may result in a coating having similar or improved mechanical properties, such as hardness, compared to compositions cured under conventional electric oven conditions. For example, the methods disclosed herein may result in a coating having a Shore A hardness, measured after the coating cooled to ambient temperature and at least 20 minutes following the exposure to the EMR and according to ASTM D2240-15, of at least 20, such as at least 25, such as at least 30, such as at least 35, such as at least 40. 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 25, such as at least 30, such as at least 35, such as at least 40, such as at least 45. 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 25, suchas at least 30, such as at least 35, such as at least 40, such as at least 45, such as at least 50. The methods disclosed herein also may result in a coating having a Shore A hardness, measured 1 day following the exposure to the EMR and according to ASTM D2240-15 of at least 50, such as at least 55, such as at least 60, such as at least 65.

[0145] It was surprisingly and unexpectedly discovered that exposure of a solvent borne composition disclosed herein to EMR generated by a diode laser and having a wavelength of 900 nm to 1,080 nm, such as 960 nm to 985 nm, may require a total energy density to ramp and maintain the composition at a temperature of 100°C for at least 5 minutes of less than 1,700 J / cm2, such as less than 1,500 J / cm2, such as less than 1,200 J / cm2, such as less than 1,000 J / cm2. It was also surprisingly and unexpectedly discovered the total energy density required to ramp and maintain a waterborne compositions disclosed herein comprising a photothermally active material at a temperature setpoint of 100°C, such as 140°C, for at least 15 minutes was reduced by at least 5%, such as by at least 10%, such as by at least 25%, such as by at least 40%, such as by at least 50% compared to total energy density required to ramp and maintain the same composition that did not include a photothermally active material at the temperature setpoint for at least 15 minutes.

[0146] These results surprisingly and unexpectedly demonstrate that exposure of the compositions disclosed herein to EMR generated by a laser and / or an LED may provide cure on demand without negatively impacting mechanical properties of the resulting coating. Thus, it was surprisingly and unexpectedly found that curing compositions by exposure to EMR generated by a laser and / or an LED may be advantageous to achieve cure on demand, while maintaining a mechanically robust coating. As used herein, “cure on demand” refers to a composition whose cure rate and / or degree of cure, as measured by Konig hardness, Shore A hardness, and / or MEK double rubs as a function of time, for example, can be accelerated by exposing the composition to EMR having a wavelength of 900 nm to 1,080 nm, such as 965 nm to 985 nm.Substrates

[0147] 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, suchas 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, munitions, missiles, electronics, and electronic components, including housings and circuit boards, glass, sports equipment, including golf balls, large and / or immovable objects such as stadiums, buildings, bridges, containers, such as food and beverage containers, and the like.

[0148] 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, and / or steel coated with a zinc-aluminum alloy. 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, and / or cast or forged metals and alloys 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.

[0149] Non-metallic substrates include polymeric, plastic, polyester, polyolefin, polyamide, cellulosic, polystyrene, polyacrylic, poly(ethylene naphthalate), polypropylene,polyethylene, nylon, EVOH, polylactic acid, other “green” polymeric substrates, poly(cthylcnctcrcphthalatc) (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, and 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.

[0150] “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, and / 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.

[0151] 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 structure, wind turbine, storage tank, nuclear plant, wall, pier, dock, levee, dam, shipping container, trailer, and / or any metal structure that is exposed to a corrosive environment.

[0152] Because the source of EMR can be portable (handheld), a portion of a structure can be coated in the field and / or on existing structures.

[0153] 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, blasted, such as sand blasting, ultrasonically cleaned, solvent wiped, roughened, plasma cleaned or etched, exposed to chemical vapor deposition, treated with an adhesion promoter, plated, anodized, annealed, and / or cladded prior to application of thecomposition. 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 coating composition. As used herein, “plating” refers to depositing a metal over a surface of the substrate.Definitions

[0154] For purposes of this detailed description, it is to be understood that the disclosure may assume alternative variations and step sequences, except where expressly specified to the contrary.

[0155] The numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard variation found in their respective testing measurements.

[0156] 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.

[0157] 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, ingredients or method steps. As used herein, “consisting of’ is understood in the context of this application to exclude the presence of any unspecified element, ingredient or method step. As used herein, “consisting essentially of’ is understood in the context of this application to include the specified elements, materials, ingredients or method steps “and those that do not materially affect the basic and novel characteristic(s)” of what is being described.

[0158] 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.

[0159] 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 otherintervening coating layers or films of the same or different composition located between the composition and the substrate surface.

[0160] As used herein, a “composition” refers to a solution, mixture, or dispersion. The composition may, in its cured state, form a coating. As used herein, a “coating” refers to a film, a layer, and the like.

[0161] As used herein, a “sealing composition” refers to a composition that, when cured, forms a sealant.

[0162] 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, and other liquid and gasses. The compositions disclosed herein may be useful, e.g., as aerospace sealants and linings for fuel tanks.

[0163] As used herein, an “adhesive composition” refers to a composition that, when cured, forms an adhesive.

[0164] As used herein, an “adhesive” refers to a cured coating that produces a loadbearing joint.

[0165] As used herein, “ambient” conditions generally refer to room temperature (e.g., 23 °C) and humidity conditions or temperature and humidity conditions that are typically found in the area in which the composition is applied to a substrate, e.g., at 10°C to 40°C and 5% to 80% relative humidity.

[0166] 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 (101,325 Pa) for 60 minutes.

[0167] As used herein, the term “cure,” “curing,” and similar terms, means that the components that form the composition begin to crosslink (i.e., interact and / or react) to form a coating or a bond. 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.

[0168] As used herein, a “gap filler composition” refers to a composition that, when cured, forms a gap filler.

[0169] As used herein, a “gap filler” refers to a coating that fills a gap.

[0170] As used herein, a “pottant composition” refers to a composition that, when cured, forms a pottant.

[0171] As used herein, a “pottant” refers to an encapsulant.

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

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

[0174] As used herein, a “pre-preg” refers to a composition pre-impregnating reinforcement fibers prior to cure.

[0175] As used herein, “monomer” refers to a molecule which can undergo polymerization, thereby contributing repeat units to the structure of a prepolymer or a polymer, as defined in Pure and Applied Chemistry, 1996, 68, 2287 (2289), “Glossary of basic terms in polymer science (IUPAC Recommendations 1996).”

[0176] As used herein, “prepolymer” refers to a molecule comprising a reaction product of two or more molecules that can be further polymerized or crosslinked.

[0177] As used herein, “polymer” refers to oligomers, homopolymers, and copolymers.

[0178] As used herein, the term “monofunctional” means an atom or molecule that is only capable of reacting to form one new bond.

[0179] As used herein, the term “polyfunctional” means an atom or a molecule that is capable of reacting to form more than one new bond more than one time through the same atom and / or through multiple single reactions of atoms within the molecule. For clarity, polyfunctional includes difunctional.

[0180] As used herein, a dash (“ — ”) that is not between two letters or symbols is used to indicate a point of bonding for a substituent or between two atoms. For example, — CONH2 is bonded to another chemical moiety through the carbon atom.

[0181] As used herein, “alkoxy” refers to an — 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.

[0182] As used herein, “alkyl” refers to an aliphatic hydrocarbon group which may be straight or branched and comprising 1 to 20 carbon atoms in the chain. Non-limiting examples of suitable alkyl groups contain 1 to 18 carbon atoms in the chain, or 1 to 6 carbon atoms in thechain. Branched means that one or more lower alkyl groups such as methyl, ethyl or propyl, are attached to a linear’ alkyl chain. “Lower alkyl” means a group having 1 to 6 carbon atoms in the chain which may be straight or branched. “Alkyl” may be unsubstituted or optionally substituted by one or more substituents which may be the same or different, each substituent being independently selected from the group consisting of halo, alkyl, aryl, cycloalkyl, cyano, hydroxy, alkoxy, alkylthio, amino, — NH(alkyl), — NH(cycloalkyl), — N(alkyl)2, carboxy, and / or — C(O)O-alkyl. Non-limiting examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl and t-butyl.

[0183] As used herein, the term “total energy density” refers to the total energy delivered divided by the area illuminated by the light source (energy per unit area), normally expressed as J / cm2.

[0184] 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 only present 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 only present 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.

[0185] In view of the foregoing description the present disclosure thus relates in particular to the following Aspects 1 to 129 without being limited thereto.

[0186] Aspect 1. A method of curing a composition comprising; exposing the composition to electromagnetic radiation (EMR) generated by a laser and / or a light emitting diode (LED) to cure the composition; wherein the composition comprises (a) an isocyanate-containing compound and (b) an active hydrogen-containing compound.

[0187] 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) an isocyanate-containing compound and (b) an active hydrogcn-containing compound.

[0188] Aspect 3. The method of aspect 1 or aspect 2, wherein the EMR comprises visible light and / or near infrared light.

[0189] 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.

[0190] Aspect 5. The method of any of the preceding aspects, wherein the EMR comprises a wavelength of at least 960 nm.

[0191] 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.

[0192] 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.

[0193] 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.

[0194] 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.

[0195] Aspect 10. The method of any of the preceding aspects, wherein the EMR comprises a wavelength of 960 nm to 985 nm.

[0196] 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.

[0197] Aspect 12. The method of any of the preceding aspects, wherein the EMR is directional.

[0198] Aspect 13. The method of any of the preceding aspects, wherein the EMR comprises monochromatic light and / or polychromatic light.

[0199] Aspect 14. The method of any of the preceding aspects, wherein the EMR is coherent.

[0200] Aspect 15. The method of any of aspects 1 and 3 to 14, wherein the laser and / or the LED is defocused.

[0201] Aspect 16. The method of any of the preceding aspects, wherein the laser generates diffuse EMR, divergent EMR, and / or collimated EMR.

[0202] 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.

[0203] 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.

[0204] 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.

[0205] 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.

[0206] Aspect 21. The method of any of the preceding aspects, wherein the laser has a wall plug efficiency of 30 percent to 80 percent, such as 50 percent to 80 percent.

[0207] Aspect 22. The method of any of aspects 1 to 18, 20, and 21, wherein the laser has a wall plug efficiency of 60 percent to 80 percent.

[0208] Aspect 23. The method of any of aspects 1 to 18, wherein the laser has a wall plug efficiency of 30 percent to 50 percent.

[0209] 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.

[0210] Aspect 25. The method of any of the preceding aspects, wherein the unit comprising the laser and / or the LED further comprises an amplifier, a temperature sensor, and / or an IR sensor.

[0211] Aspect 26. The method of any of the preceding aspects, wherein the temperature sensor controls a temperature of the composition temperature, a temperature of a substrate, and / or a ramp rate.

[0212] 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.

[0213] Aspect 28. The method of any of the preceding aspects, wherein the laser and / or the LED comprises a portable device, a hand-held device, and / or a robotically guided device.

[0214] Aspect 29. The method of any of the preceding aspects, wherein the composition further comprises a photothermally active material.

[0215] Aspect 30. The method of aspect 29, wherein the photothermally active material comprises carbon black, copper phthalocyanine, silicon carbide, and / or manganese dioxide.

[0216] Aspect 31. The method of aspect 29 or aspect 30, werein 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.

[0217] Aspect 32. The method of any of aspects 29 to 31, 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.

[0218] Aspect 33. The method of any of aspects 29 to 32, 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.

[0219] Aspect 34. The method of any of aspects 29 to 32, wherein the composition comprises the photothermally active material in an amount of no more than 10 percent by weight based on total solids weight of the composition.

[0220] Aspect 35. The method of any of aspects 29 to 31 and 33, 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.

[0221] Aspect 36. The method of any of aspects 29 to 32, 34 and 35, 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.

[0222] Aspect 37. The method of any of the preceding aspects, wherein the isocyanate- containing compound comprises a monofunctional isocyante-containing compound, a polyfunctional isocyanate-containing compound, a monomer, a small molecule, a prepolymer, and / or a polymer.

[0223] Aspect 38. The method of any of the preceding aspects, wherein the isocyanate- containing compound comprises a blocked isocyanate-containing compound.

[0224] Aspect 39. The method of any of the preceding aspects, wherein the isocyanate- containing compound comprises an unblocked isocyanate-containing compound.

[0225] Aspect 40. The method of any of the preceding aspects, wherein the composition comprises the isocyanate-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.

[0226] Aspect 41. The method of any of the preceding aspects, wherein the composition comprises the isocyanate-containing compound in an amount of at least 5 percent by weight based on total solids weight of the composition.

[0227] Aspect 42. The method of any of the preceding aspects, wherein the composition comprises the isocyanate-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.

[0228] Aspect 43. The method of any of the preceding aspects, wherein the composition comprises the isocyanate-containing compound in an amount of no more than 85 percent by weight based on total solids weight of the composition.

[0229] Aspect 44. The method of any of the preceding aspects, wherein the composition comprises the isocyanate-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.

[0230] Aspect 45. The method of any of aspects 1 to 39 or 41 to 44, wherein the composition comprises the isocyanate-containing compound in an amount of 5 percent by weight to 85 percent by weight based on total solids weight of the composition.

[0231] Aspect 46. The method of any of the preceding aspects, wherein the active hydrogen-containing compound comprises a hydroxyl-containing compound, an amine- containing compound, and / or a thiol-containing compound.

[0232] Aspect 47. The method of aspect 46, wherein the thiol-containing compound has thiol equivalent weight of at least 80 g / eq, such as at least 100 g / eq.

[0233] Aspect 48. The method of aspect 46 or aspect 47, wherein the thiol-containing compound has a thiol equivalent weight of at least 125 g / eq, such as at least 400 g / eq.

[0234] Aspect 49. The method of any of aspects 46 to 48, wherein the thiol-containing compound has a thiol equivalent weight of no more than 4,000 g / eq, such as no more than 2,500 g / eq.

[0235] Aspect 50. The method of any of aspects 46 to 49, wherein the thiol-containing compound has a thiol equivalent weight of no more than 2,000 g / eq, such as no more than 1,650 g / eq.

[0236] Aspect 51. The method of any of aspects 46 to 50, wherein the thiol-containing compound has a thiol equivalent weight of 80 g / eq to 4,000 g / eq, such as 100 g / eq to 2,500 g / eq.

[0237] Aspect 52. The method of any of aspects 46 to 51, wherein the thiol-containing compound has a thiol equivalent weight of 125 g / eq to 2,000 g / eq, such as 400 g / eq to 1,650 g / eq.

[0238] Aspect 53. The method of any of the preceding aspects, wherein the active hydrogen-containing compound is blocked, unblocked, encapsulated, and / or unencapsulated.

[0239] Aspect 54. The method of any of the preceding aspects, wherein the active hydrogen-containing compound comprises a monomeric compound and / or a polymeric compound.

[0240] Aspect 55. The method of any of the preceding aspects, wherein the composition comprises the active hydrogen-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.

[0241] Aspect 56. The method of any of the preceding aspects, wherein the composition comprises the active hydrogen-containing compound in an amount of at least 5 percent by weight based on total solids weight of the composition.

[0242] Aspect 57. The method of any of the preceding aspects, wherein the composition comprises the active hydrogen-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.

[0243] Aspect 58. The method of any of the preceding aspects, wherein the composition comprises the active hydrogen-containing compound in an amount of no more than 85 percent by weight based on total solids weight of the composition.

[0244] Aspect 59. The method of any of the preceding aspects, wherein the composition comprises the active hydrogen-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.

[0245] Aspect 60. The method of any of aspects 1 to 54 and 56 to 59, wherein the composition comprises the active hydrogen-containing compound in an amount of 5 percent by weight to 85 percent by weight based on total solids weight of the composition.

[0246] Aspect 61. The method of any of the preceding aspects, wherein the composition further comprises an accelerator, such as an amine-based catalyst, a nitrogen-based catalyst, an organic acid, an organometallic complex, and / or a Lewis acid catalyst.

[0247] Aspect 62. The method of aspect 61, 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 0.01 percent by weight.

[0248] Aspect 63. The method of aspect 61 or aspect 62, wherein the composition comprises the accelerator in an amount of at least 0.1 percent by weight based on total solids weight of the composition.

[0249] Aspect 64. The method of any of aspects 61 to 63, 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 8 percent by weight.

[0250] Aspect 65. The method of any of aspects 61 to 64, 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 0.01 percent by weight to 8 percent by weight.

[0251] Aspect 66. The method of any of aspects 61 to 65, wherein the composition comprises the accelerator in an amount of 0.01 percent by weight to 5 percent by weight based on total solids weight of the composition, such as 0.1 percent by weight to 5 percent by weight.

[0252] Aspect 67. The method of any of the preceding aspects, wherein the composition further comprises an additive, a filler, and / or a solvent.

[0253] Aspect 68. The method of aspect 67, wherein the additive comprises a rheology modifier, a reactive diluent, a non-reactive diluent, a dispersant, a tackifier, a thermoplastic polymer, a surfactant, a flame retardant, a corrosion inhibitor, a UV stabilizer, a hindered amine light stabilizer (HALS), a colorant, a tint, a plasticizer, an adhesion promoter, and / or a moisture scavenger.

[0254] Aspect 69. The method of aspect 67 or aspect 68, 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.

[0255] Aspect 70. The method of any of aspects 67 to 69, wherein the composition comprises the additive in an amount of no more than 20 percent by weight based on total solids weight of the composition, such as no more than 10 percent by weight.

[0256] Aspect 71. The method of any of aspects 67 to 70, wherein the composition comprises the additive in an amount of 0.01 percent by weight to 20 percent by weight based on total solids weight of the composition, such as 0.1 percent by weight to 10 percent by weight.

[0257] Aspect 72. The method of any of aspects 67 to 71, 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.

[0258] Aspect 73. The method of any of aspects 67 to 72, wherein the composition comprises the filler in an amount of no more than 30 percent by weight based on total solids weight of the composition, such as no more than 20 percent by weight.

[0259] Aspect 74. The method of any of aspects 67 to 73, wherein the composition comprises the filler in an amount of 0.1 percent by weight to 30 percent by weight based on total solids weight of the composition, such as 1 percent by weight to 20 percent by weight.

[0260] Aspect 75. The method of any of aspects 67 to 74, wherein the solvent comprises water.

[0261] Aspect 76. The method of any of aspects 67 to 75, wherein the solvent comprises an organic solvent.

[0262] Aspect 77. The method of any of aspects 67 to 76, wherein the composition comprises the solvent in an amount of at least 1 percent by weight based on total weight of the composition, such as at least 30 percent by weight.

[0263] Aspect 78. The method of any of aspects 67 to 77, wherein the composition comprises the solvent in an amount of no more than 90 percent by weight based on total weight of the composition, such as no more than 60 percent by weight.

[0264] Aspect 79. The method of any of aspects 67 to 78, wherein the composition comprises the solvent in an amount of 1 percent by weight to 90 percent by weight based on total weight of the composition, such as 30 percent by weight to 60 percent by weight.

[0265] Aspect 80. The method of any of the preceding aspects, wherein the composition has a total solids content of at least 10 percent by weight based on total weight of the composition, such as at least 30 percent by weight.

[0266] Aspect 81. The method of any of the preceding aspects, wherein the composition has a total solids content of up to 100 percent by weight based on total weight of the composition.

[0267] Aspect 82. The method of any of the preceding aspects, wherein the composition has a total solids content of no more than 99 percent by weight based on total weight of the composition.

[0268] Aspect 83. The method of any of the preceding aspects, wherein the composition has a total solids content of 10 percent by weight to 100 percent by weight based on total weight of the composition, such as 30 percent by weight to 100 percent by weight.

[0269] Aspect 84. The method of aspects 1 to 79, wherein the composition has a total solids content of 100 percent by weight based on total weight of the composition.

[0270] Aspect 85. The method of any of the preceding aspects, wherein the composition is substantially free, essentially free, or completely free of a photopolymerizable initiator.

[0271] Aspect 86. 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.

[0272] Aspect 87. The method of any of the preceding aspects, wherein the composition is formulated as a IK composition, a 2K composition, and / or a higher-component composition.

[0273] Aspect 88. The method of any of the preceding aspects, comprising applying the composition to a surface of a substrate, such as by extruding, pressing, grouting, caulking, spreading, brushing, rolling, troweling, dipping, and / or spraying.

[0274] Aspect 89. The method of any of the preceding aspects, wherein the composition is exposed to the EMR for at least 5 minutes, such as at least 10 minutes.

[0275] Aspect 90. The method of any of the preceding aspects, wherein the composition is exposed to the EMR for at least 15 minutes.

[0276] Aspect 91. 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.

[0277] Aspect 92. 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.

[0278] Aspect 93. 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.

[0279] Aspect 94. 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.

[0280] Aspect 95. 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.

[0281] Aspect 96. The method of any of aspects 1 to 91 and 93, 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.

[0282] Aspect 97. The method of any of aspects 1 to 91, 94, and 96, 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.

[0283] Aspect 98. The method of any of aspects 1 to 91 and 95 to 97, 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.

[0284] Aspect 99. The method of any of aspects 88 to 98, comprising cleaning and / or deoxidizing the substrate surface.

[0285] Aspect 100. The method of any of aspects 88 to 99, 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.

[0286] Aspect 101. The method of any of the preceding aspects, wherein the substrate comprises a fixed structure.

[0287] Aspect 102. The method of any of aspects 88 to 101, comprising applying the composition to a damaged portion of the surface of the substrate.

[0288] Aspect 103. The method of any of aspects 88 to 102, wherein the surface comprises a pre-existing coating, and wherein the pre-existing coating is at least partially removed prior to the applying.

[0289] Aspect 104. The method of any of aspects 88 to 103, wherein a temperature of the substrate and / or the surface of the substrate does not increase upon the exposure to EMR, such as wherein the temperature of the surface of the substrate does not exceed 121°C.

[0290] Aspect 105. The method of any of aspects 88 to 104, 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.

[0291] Aspect 106. The method of any of the preceding aspects, further comprising flashing the composition prior to the exposure to the EMR.

[0292] Aspect 107. The method of any of the preceding aspects, wherein a total energy density of less than 700 J / cm2is required to cure the coating, such as less than 475 J / cm2.

[0293] Aspect 108. The method of any of the preceding aspects, wherein a total energy density of less than 375 J / cm2is required to cure the coating, such as less than 300 J / cm2.

[0294] Aspect 109. The method of any of aspects 29 to 108, 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%.

[0295] Aspect 110. The method of any of aspects 29 to 109, wherein a total energy density required to cure the composition was reduced by at least 35% compared to a total energy density required to cure a composition that did not comprise the photothermally active material, such as reduced by at least 40%.

[0296] Aspect 111. The method of any of aspects 1 to 106, wherein a total energy density of less than 1,700 J / cm2is required to cure the coating, such as less than 1,500 J / cm2.

[0297] Aspect 112. The method of any of aspects 1 to 106 and 111, wherein a total energy density of less than 1,200 J / cm2is required to cure the coating, such as less than 1,000 J / cm2.

[0298] Aspect 113. The method of any of aspects 29 to 106, 111, and 112, 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%.

[0299] Aspect 114. The method of any of aspects 29 to 106 and 111 to 113, wherein a total energy density required to cure the composition was reduced by at least 25% compared to atotal energy density required to cure a composition that did not comprise the photothermally active material, such as reduced by at least 40%.

[0300] Aspect 115. The method of any of aspects 29 to 106 and 111 to 114, wherein a total energy density required to cure the composition was reduced by at least 50% compared to a total energy density required to cure a composition that did not comprise the photothermally active material.

[0301] Aspect 116. The method of any of aspects 26 to 115, wherein a temperature of the substrate following exposure to the EMR is below a heat deflection temperature of the substrate.

[0302] Aspect 117. A substrate comprising a coating formed from the composition cured by the method of any of the preceding aspects.

[0303] Aspect 118. The substrate of aspect 117, wherein the coating comprises a sealant, an adhesive, a gap filler, a pottant, a prepreg, and / or a liquid shim.

[0304] Aspect 119. The substrate of aspect 117 or aspect 118, wherein the coating has a Konig hardness of at least 149, such as a Konig hardness of at least 165; wherein the Konig hardness is measured at least 20 minutes following termination of the exposure to the EMR according to ASTM D4366.

[0305] Aspect 120. The substrate of any of aspects 117 to 119, wherein the coating has a Konig hardness of at least 170, such as a Konig hardness of at least 175; wherein the Konig hardness is measured at least 20 minutes following termination of the exposure to the EMR according to ASTM D4366.

[0306] Aspect 121. The substrate of any of aspects 117 to 120, wherein the coating has a Konig hardness of at least 180; wherein the Konig hardness is measured at least 20 minutes following termination of the exposure to the EMR according to ASTM D4366.

[0307] Aspect 122. The substrate of any of aspects 117 to 121, wherein the coating achieves 100 MEK double rubs; wherein the MEK double rubs are measured at least 20 minutes following termination of the exposure to the EMR and performed according to ASTM D5402-19.

[0308] Aspect 123. The substrate of any of aspects 117 to 122, wherein the coating has a Shore A hardness of at least 20, such as a Shore A hardness of at least 25; wherein the Shore A hardness is measured at least 20 minutes following termination of the exposure to the EMR according to ASTM D2240-15.

[0309] Aspect 124. The substrate of any of aspects 117 to 123, wherein the coating has a Shore A hardness of at least 30, such as a Shore A hardness of at least 35; wherein the Shore A hardness is measured at least 20 minutes following termination of the exposure to the EMR according to ASTM D2240-15.

[0310] Aspect 125. The substrate of any of aspects 117 to 124, wherein the coating has a Shore A hardness of at least 25, such as a Shore A hardness of at least 35; wherein the Shore A hardness is measured at least 1 hour following termination of the exposure to the EMR according to ASTM D2240-15.

[0311] Aspect 126. The substrate of any of aspects 117 to 125, wherein the coating has a Shore A hardness of at least 25, such as a Shore A hardness of at least 35; wherein the Shore A hardness is measured at least 3 hours following termination of the exposure to the EMR according to ASTM D2240-15.

[0312] Aspect 127. The substrate of any of aspects 117 to 126, wherein the coating has a Shore A hardness of at least 40, such as a Shore A hardness of at least 45; wherein the Shore A hardness is measured at least 3 hours following termination of the exposure to the EMR according to ASTM D2240-15.

[0313] Aspect 128. The substrate of any of aspects 117 to 127, wherein the coating has a Shore A hardness of at least 50, such as a Shore A hardness of at least 55; wherein the Shore A hardness is measured at least 1 day following termination of the exposure to the EMR according to ASTM D2240-15.

[0314] Aspect 129. The substrate of any of aspects 117 to 128, wherein the coating has a Shore A hardness of at least 60, such as a Shore A hardness of at least 65; wherein the Shore A hardness is measured at least 1 day following termination of the exposure to the EMR according to ASTM D2240-15.

[0315] Illustrating the disclosure are the following examples, which, however, are not to be considered as limiting the disclosure to their details.Examples

[0316] Laser: The defocused laser unit used for all studies was a Compact Heating and Drying SYS-CD system supplied by IPG Photonics® Corporation (Marlborough, MA) outfitted with 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).Example 1 : Water-Borne Two-Component Polyurethane CoatingsTable 1: Waterborne Acrylic Clear Base (Example A)

[0317] The waterborne acrylic clear base (Example A) was prepared using the components in the specified amounts provided in Table 1. Component 1 was weighed into a pint can. Under agitation, Components 2-7 were added, in order, and mixed for 10 minutes.Table 2: Waterborne Acrylic White Base (Example B)7Polymeric dispersant8Colorant

[0318] The waterborne acrylic white base (Example B) was prepared using the components in the specified amounts set forth in Table 2. Components 1-6 were weighed in aglass jar. Materials were agitated until homogenous before adding Component 7. Then, 2.0 mm aluminum oxide grind media (Grade BA0211, commercially available from MSE Supplies, LLC) was added to the glass jar at a level of 50% by weight based on total weight of the grind paste (Components 1-7). The glass jar was placed onto the Lau disperser for 90 minutes until a Hegman grind of 7 was reached. The grind media was then filtered, and the paint was placed into a pint can. Under agitation, Components 8-9 were added, in order, and mixed for 10 minutes.Table 3: Waterborne Acrylic Black Base (Example C)9Specialty carbon black pigment (a photothermally active material)

[0319] The waterborne acrylic black base (Example C) was prepared using the components in the amounts specified in Table 3. Components 1-6 were weighed into a glass jar. Materials were agitated until homogenous prior to adding Component 7. 2.0 mm aluminum oxide grind media was added to the glass jar at a level of 50% by weight based on total weight of the grind paste (Components 1-7). The glass jar was placed onto the Lau disperser for 90 minutes until a Hegman grind of 6.5 was reached. Next, the grind media was filtered, and the paint was placed into a pint can. Under agitation, Components 8-9 were added, in order, and mixed for 10 minutes.Table 4: Isocyanate Hardener10Aliphatic Poly isocyanate resin based on HMDI11Ester of dicarboxylic acid (solvent, plasticizer, additive)

[0320] The isocyanate hardener was prepared using the components in the amounts specified in Table 4. Components 1 and 2 were added to a glass jar and stirred until homogenous.Table 5: Sample Compositions 1 to 6Formulation for Water-Borne Two-Component Polyurethane Coatings Samples 1-6

[0321] Each sample was prepared by first weighing each respective base (Examples A-C) into a glass jar. Samples 4-6 were placed onto the Lau disperser for 10 minutes to ensure a homogenous mixture. Then, the isocyanate hardener (and deionized water in Samples 1, 4, and 6) were added to each jar and hand stirred until homogenous.Test Sample Preparation

[0322] After thorough mixing, a drawdown of each sample was made using an 8 mil Byk-Gardner drawdown bar. The substrate used to create these examples was cold rolled steel with B1000 / P99X pretreatment (ACT Item #40821, ACT Test Panels LLC) then powder coated with PCTA89105 RAL 9010 Pure White (PPG Industries, Inc.).

[0323] Oven-Exposed Samples. Panels having a drawndown sample of one of Samples 1 to 6 were then flashed for 10 minutes at ambient conditions and were cured using a conventional electric oven at 100°C for 5 minutes.

[0324] Laser-Exposed Samples. Panels having a drawndown sample of one of Samples 1 to 6 were then flashed for 10 minutes at ambient conditions and were then placed in the laser unit described above. Samples were exposed to the EMR with a 30 second ramp from ambient to 100°C and then held at 100°C for 5 minutes.

[0325] Oven-exposed and laser-exposed samples were cooled to room temperature before testing, at which point the degree of cure was measured using MEK (methyl ethyl ketone) double rubs in accordance with ASTM D5402-19. An MEK-soaked towel was rubbed across the surface of the panel until the coating failed, or 100 double rubs were achieved, whichever occurred first. Results are provided in Table 6.

[0326] Dry film thickness was measured using a hand-held, magnetic inductive film thickness gauge (Fischer Dualscope® DMP40). Results are provided in Table 6. The Konig hardness was measured using a Pendulum Hardness Tester (catalog # 5865 from BYK-Gardner GmbH) in accordance with ASTM D4366. Results are provided in Table 6.Table 6: ResultsResults and Discussion

[0327] The results of the testing showed an improvement in cure response when samples were cured in the laser unit compared to the electric oven, as demonstrated by the Konig hardness values. Example 7, which was cured with the laser unit, required more MEK double nibs than Example 1, which was cured with the electric oven, to cause coating failure. In addition, using carbon black in the coating layer decreased the total energy density needed to maintain the coating at temperature, as shown in Example 9. The clear and white samples, shown in Examples 7 and 8, respectively, had a higher total energy density than Example 9 which contained carbon black. Incorporating even a small amount of carbon black in clear or white samples (Examples 10-12) demonstrated a significant reduction in the total energy density needed to maintain the coating temperature.Example 2: 100% Solids Two-Component Polyurethane CoatingsTable 7: 100% Solids Isocyanate-Alcohol Formulation Examples1MDI prepolymer from Covestro AG2Dimer diol from Cargill, Inc.3Tri-functional polyol from BASF4Molecular sieve zeolite from Zeochem LLC5Astrad IS PCN blue contains copper phthalocyanine from Penn Color, Inc. (photothermally active material)6Manganese dioxide from Shepherd Technologies (photothermally active material)7Regal 660R carbon black from Cabot Corporation (photothermally active material)8Dibutyltin dilaurate from Songwon Ind.Formulation for 100% Solids Isocyanate-Alcohol Examples 13-20

[0328] The individual parts (Base Pack and Hardener Pack) were prepared and mixed using a Speedmix DAC mixer, model 600.1 FVZ. The Hardener Pack was prepared by combining all the listed components in Table 7, in the order and amounts listed. After all components were added, samples were mixed on the DAC mixer for 2 minutes at 1800 rpm. The mixture was inspected and mixed manually as needed with a spatula to ensure homogeneity.Test Sample Preparation

[0329] The Base and Hardener Packs were hand-mixed in the total values listed in Table 7, then subsequently cast into 1” diameter pucks on aluminum weigh pans for all hardness testing. Adhesion samples were drawn down on MEK-cleaned 2024-T3 substrates. Cure of the samples was monitored for 24 hours with a final Shore A hardness, measured according to ASTM D2240-15 and reported in Tables 8-10 below.

[0330] Laser Exposed Samples. Panels having a drawndown sample of one of Samples 1 to 6 were then flashed for 10 minutes at ambient conditions and were then placed in the laser unit described above. Samples were exposed to the EMR with a 30 second ramp from ambient to 60°C and then held at 60°C for 10 minutes, then checked for Shore A hardness. Results are provided in Table 8.

[0331] Oven Exposed Samples. Samples were exposed to an oven set at 60°C for 10 minutes, then checked for Shore A hardness. Results are provided in Table 9.

[0332] Ambient-Cured Samples. Samples were placed in an environment-controlled cabinet at 25°C with 50% relative humidity (Thermofisher Forma #3940), then checked for Shore A hardness at the times specified in Table 10. Results are provided in Table 10.

[0333] FIGS. 1 to 8 show the Shore A hardness of Examples 13 to 20, respectively, across the three cure conditions.Table 8: Shore A Hardness Cure Profile Post Laser Exposure

[0334] The data in Table 8 demonstrate that all the samples began to cure within 20 minutes after EMR exposure. Additionally, comparable Shore A hardness was observed across all examples, demonstrating that the addition of the photothcrmally active material did not negatively impact Shore A hardness.Table 9: Shore A Hardness Cure Profile Post Oven Exposure

[0335] The data in Table 9 demonstrate that all Examples 13 to 20 had low cure 20 minutes following exposure to the oven. Cure for all the samples continued 1 day followingexposure, as indicated by the increase in Shore A hardness from 3 hours post-exposure to 1 -day post-exposure. Examples 13 and 15 to 20 demonstrated increased Shore A hardness when cured by EMR exposure (data provided in Table 8) compared to the Shore A hardness when cured by oven exposure. For example, Example 16 demonstrated a 1-day Shore A hardness of 65 when cured by laser and a 1-day Shore A hardness of 55 when cured by oven (an 18% increase in Shore A hardness 1 day following exposure to cure conditions).Table 10: Shore A Hardness Cure Profile Under Ambient Conditions

[0336] The data in Table 10 demonstrates the Shore A hardness of Examples 13-20 when cured under ambient conditions. The ambient-cured examples exhibited little to no cure at 20 minutes. Only Examples 19 and 20 demonstrated some cure at 1 hour, as indicated by the Shore A hardness measurements. Therefore, Examples 13-20 demonstrated substantially faster cure when exposed to EMR compared to being cured at ambient conditions, as demonstrated by comparing the data in Tables 8 and 10.

[0337] As shown by the data provided in Table 8 (laser cured), Table 9 (oven cure), and Table 10 (ambient cured), the laser-cured samples demonstrated cure at 20 minutes postexposure, while the oven-cured and ambient-cured samples demonstrated low or no cure at the same time point.Table 11: Material Performance (Summarized from Tables 8 to 10)

[0338] The data in Table 11 provide the final Shore A hardness of Examples 13 to 20 cured by laser, by oven, or in ambient conditions. As shown, the final Shore A hardness measurements for the laser-cured samples are either comparable or improved over the oven- cured and ambient-cured samples. Therefore, laser-cure results in a faster cure without compromising mechanical performance.Example 3: Solvent-Borne Two-Component Polyurethane Coatings

[0339] Total energy density. The total laser energy was calculated according to Equation I disclosed above.

[0340] Solvent resistance test. A solvent resistance test was performed by placing a coated test panel on a flat table or other suitable flat, firm surface. Two sterile gauze pads were affixed over the end of a one-pound Ball-Peen hammer. The gauze was affixed such that it was snugly held in place with a rubber band and had four layers of gauze over the end of the hammer with no wrinkles. The gauze was saturated with an appropriate solvent, such as methyl ethyl ketone (MEK), for the substrate being tested. The gauze was re-saturated every 50 double nibs. The substrate coated with the composition was immediately rubbed with the saturated gauze over the test area using a back-and-forth stroke of 2-4 inches. The weight of the hammer controlled the downward pressure. A “double rub” was defined as one forward and backward motion completed. The double rubs were continued until the bare substrate was exposed in the center of the strip where the rubs were performed or until 100 double rubs were achieved. The number of “double rubs” was recorded as the test result (MEK double rubs). The gauze was removed and replaced with new gauze in between each sample tested.

[0341] Solvent borne compositions were prepared according to the formulations in Table13.Table 13: Solvent-Borne Compositions1JONCRYL 500 available from BASF (Southfield, MI)2TRONOX CR-826, TiCh pigment available from Tronox (Stamford, CT)3Disperbyk 110 available from B YK-Chemie GmbH (Wesel, Germany)4Monarch 1300, carbon black pigment available from Cabot Corporation (Billerica, MA) (photothermally active material)5SOLSPERSE 5000S available from The Lubrizol Corporation (Wickliffe, OH)6Microgrit Silicon carbide GC2000 available from Micro Abrasives Corporation (Westfield, MA) (photothermally active material)71 wt% solution of dibutyltin dilaurate in n-butyl acetate8Aliphatic polyisocyanate (low-viscosity hexamethylene diisocyanate (HDI) trimer) available from Covestro AG (Leverkusen, Germany)Formulation of Solvent Borne Two-Component Compositions SB1 to SB9

[0342] The A-pack portion of formulations SB2 through SB9 were weighed into an 8- ounce glass jar and then 350g of Zirconox 1.0- 1.2mm diameter ceramic micro beads (available from Jyoti Ceramic Ind. Pvt. Ltd., Nashik India) were added. The jars were then placed on a Lau disperser (model DAS 200 from Lau Gmbh (Hemer, Germany)) for 1 hr. Then the formulas were filtered to remove the ceramic micro beads.Test Sample Preparation

[0343] For all formulas SB 1 to SB9, prior to application, the B-Pack was added to the A- Pack and stirred. Then the mixed formula was applied to a white substrate (pretreated steel panels (ACT 40821 B1000 P99X from ACT Test Panels (Hillsdale, MI)) with a cured coating of PCTA89105 RAL 9010 Pure White, available from PPG Industries, Inc. (Pittsburgh, PA)) using a 5-mil gap, 4-inch wide square drawdown bar. Once the formula was applied to the substrate, it was allowed to flash at ambient conditions for 5 minutes and then placed into the desired cure method (laser cure or thermal convection oven cure).

[0344] Oven Exposed Samples. Convection oven cure was carried out by placing the coated substrate in a 100°C oven for 15 minutes.

[0345] Laser Exposed Samples. For laser cure, the coated substrate was irradiated with 975 nm light using the laser unit described above with a 30 second ramp from ambient to 100°C and then held at 100°C for 15 minutes.Results and Discussion

[0346] All samples reached 100 MEK double rubs with both cure methods. However, when cured with the laser method, there were differences in total energy density as shown in Table 13.

[0347] As shown in Table 13, SB2 takes more energy to cure than SB1. When comparing SB3 to SB2, the incorporation of a photothermally active material decreases theenergy required to maintain the cure temperature. Comparing SB4 through SB6 to SB1 , incorporation of Photothcrmally Active Material A significantly reduced the total energy density required to maintain the cure temperature compared to the formula with no photothermally active material, SB1. Further, as the level of photothermally active material increased from SB4 through SB6, the total energy density required to maintain temperature was reduced. Similarly, comparing SB7 through SB9 to SB1, incorporation of Photothermally Active Material B reduced the total energy density required to maintain the cure temperature compared to the SB1 formula with no photothermally active material. Further, as the photothermally active material level increased from SB7 through SB9, the total energy density required to maintain temperature was reduced.Example 4: Solvent-Borne Two-Component Blocked Isocyanate Polyurethane Coatings

[0348] Total energy density. The total energy density was calculated as set forth above.

[0349] Solvent resistance test. The solvent resistance was measured as set forth in Example 3.

[0350] The compositions were prepared according to the formulations provided in Table14.Table 14: Blocked Isocyanate Polyurethane Composition Formulations1JONCRYL 500 available from BASF (Southfield, MI)2TRONOX CR-826, TiC>2 pigment available from Tronox (Stamford, CT)3Disperbyk 110 available from B YK-Chemie GmbH (Wesel, Germany)4Monarch 1300, carbon black pigment available from Cabot Corporation (Billerica, MA)5SOLSPERSE 5000S available from The Lubrizol Corporation (Wickliffe, OH)6Microgrit Silicon carbide GC2000 available from Micro Abrasives Corporation (Westfield, MA)7DESMODUR BL 3475 BA / SN, diethyl malonate blocked, aliphatic polyisocyanate based on HDI I IPDI available from Covestro AG (Leverkusen, Germany)Formulation of Blocked Isocyanate Polyurethane Compositions SB 10 to SB 18

[0351] The A-pack portion of formulations SB 11 through SB 18 were weighed into an 8- ounce glass jar and then 350g of Zirconox 1.0- 1.2mm diameter ceramic micro beads (available from Jyoti Ceramic Ind. Pvt. Ltd., Nashik India) were added. The jars were then placed on a Lau disperser (model DAS 200 from Lau Gmbh (Hemer, Germany)) for 1 hr. Then, the formulas were filtered to remove the ceramic micro beads.Test Sample Preparation

[0352] For all formulas SB 10 to SB 18, prior to application, the B-Pack was added to the A-Pack and stirred. Then, the mixed formula was applied to a white substrate (pretreated steel panels (ACT 40821 B1000 P99X from ACT Test Panels (Hillsdale, MI)) with a cured coating of PCTA89105 RAL 9010 Pure White, available from PPG Industries, Inc. (Pittsburgh, PA) using a 5-mil gap, 4-inch wide square drawdown bar. Once the formula was applied to the substrate, it was allowed to flash at ambient conditions for 5 minutes and then placed into the desired cure method (laser cure or thermal convection oven cure).

[0353] Oven Exposed Samples. Convection oven cure was carried out by placing the coated substrate in a 140°C oven for 15 minutes.

[0354] Laser Exposed Samples. For laser cure, the coated substrate was irradiated with 975 nm light using the laser unit described above with a 30 second ramp from ambient to 140°C and then held at 140°C for 15 minutes.Results and Discussion

[0355] The samples cured with the convection oven ranged between 71 to 100 MEK double rubs depending on the formula. Only the white formulas reached 100 MEK double rubs. In contrast, all laser-cured samples reached 100 MEK double rubs, showing an advantage over the oven cure. When cured with the laser method, the differences in observed total energy density are shown in Table 14.

[0356] As shown in Table 14, SB 11 with white pigment takes more energy to cure than SB 10, which is a clear coating. Not wishing to be bound by theory, TiO2 scatters the laser light and does not efficiently absorb the laser energy, requiring more energy than the unpigmented SB 10. When comparing SB 12 to SB 11, the incorporation of a photothermally active material decreases the energy required to maintain the cure temperature. Comparing SB 13 through SB 15 to SB 10, incorporation of Photothermally Active Material A significantly reduces the energy required to maintain the cure temperature as compared to SB 10, the formula without photothermally active material. Similarly, comparing SB16 through SB18 to SB10, incorporation of Photothermally Active Material B reduces the energy required to maintain the cure temperature as compared to SB 10, the formula without photothermally active material. Further, as the level of photothermally active material increased from SB16 through SB18, the energy required to maintain temperature was reduced.

[0357] Whereas specific aspects of the invention have been described in detail, it will be appreciated by those skilled in the ait 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 invention 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) an isocyanate-containing compound and (b) an active hydrogen-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 further comprises a pho to thermally active material.

7. The method of claim 6, wherein the photothermally active material comprises carbon black, copper phthalocyananine, silicon carbide, and / or manganese dioxide.

8. The method of claim 6 or claim 7, 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.

9. The method of any of the preceding claims, wherein the composition is exposed to the EMR for at least 5 minutes.

10. The method of any of the preceding claims, wherein a total energy density of less than 1,700 J / cm2is required to cure the coating, such as less than 700 J / cm2.

11. The method of any of claims 6 to 10, wherein 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 25%.

12. The method of any of the preceding claims, wherein the laser is a mobile device, a handheld device, and / or a robotically guided device.

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

14. The method of claim 13, further comprising cleaning, deoxidizing, abrading, and / or pretreating the surface of the substrate prior to the applying.

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

16. The substrate of claim 15, wherein the coating:(a) has a Konig hardness of at least 149 measured at least 20 minutes following termination of the exposure to the EMR;(b) achieves 100 MEK double rubs measured at least 20 minutes following termination of the exposure to the EMR;(c) has a Shore A hairiness of at least 20 measured at least 20 minutes following termination of the exposure to the EMR(d) has a Shore A hardness of at least 35 measured at least 3 hours following termination of the exposure to the EMR; and / or(e) has a Shore A hardness of at least 50 measured at least 1 day following termination of the exposure to the EMR; wherein the Konig hardness is measured according to ASTM D4366; wherein the MEK double rubs are performed according to ASTM D5402-19; and wherein the Shore A hardness is measured according to ASTM D2240-15.

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