Methods of curing epoxy-containing compositions

Abstract

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

Description

METHODS OF CURING EPOXY-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 epoxy-containing compound using electromagnetic radiation are disclosed.BACKGROUND

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

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

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

[0006] Also disclosed are coating application kits for a two-component composition, the kit comprising: (a) a cartridge assembly comprising: (i) a cartridge containing a first component of the composition; and (ii) an injector containing a second component of the composition; wherein the cartridge and the injector are structured and arranged to allow the second component to flow into the cartridge to form a composition; and (b) instructions for exposing the composition to defocused electromagnetic radiation (EMR) generated by a laser to cure the composition.

[0007] Also disclosed are coating application kits for a two-component composition, the kit comprising: (a) a cartridge assembly comprising: (i) a cartridge comprising a firstcompartment containing a first component of the composition, a second compartment containing a second component of the composition, and a barrier separating the first compartment and the second compartment; and (ii) a piercer structured and arranged to break the barrier to allow the first component and the second component to flow together to form a composition; and (b) instructions for exposing the composition to defocused electromagnetic radiation (EMR) generated by a laser to cure the composition.BRIEF DESCRIPTION OF THE DRAWINGS

[0008] FIG. 1 is a graph showing the Shore A hardness of cured Example K as a function of time (days) and cured by laser, oven, or ambient conditions.

[0009] FIG. 2 is a graph showing the Shore A hardness of cured Example L as a function of time (days) and cured by laser, oven, or ambient conditions.

[0010] FIG. 3 is a graph showing the Shore A hardness of cured Example M as a function of time (days) and cured by laser, oven, or ambient conditions.

[0011] FIG. 4 is a graph showing the Shore A hardness of cured Example N as a function of time (days) and cured by laser, oven, or ambient conditions.

[0012] FIG. 5 is a graph showing the Shore A hardness of cured Example O as a function of time (days) and cured by laser, oven, or ambient conditions.

[0013] FIG. 6 is a graph showing the Shore A hardness of cured Example P as a function of time (days) and cured by laser, oven, or ambient conditions.

[0014] FIG. 7 is a graph showing the Shore A hardness of cured Example Q as a function of time (days) and cured by laser, oven, or ambient conditions.

[0015] FIG. 8 is a graph showing the Shore A hardness of cured Example R as a function of time (days) and cured by laser, oven, or ambient conditions.

[0016] FIG. 9 is a graph showing the Shore D hardness of cured Example S as a function of time (days) and cured by laser, oven, or ambient conditions.

[0017] FIG. 10 is a graph showing the Shore D hardness of cured Example T as a function of time (days) and cured by laser, oven, or ambient conditions.

[0018] FIG. 11 is a graph showing the Shore D hardness of cured Example U as a function of time (days) and cured by laser, oven, or ambient conditions.

[0019] FIG. 12 is a graph showing the Shore D hardness of cured Example V as a function of time (days) and cured by laser, oven, or ambient conditions.

[0020] FIG. 13 is a graph showing the Shore D hardness of cured Example W as a function of time (days) and cured by laser, oven, or ambient conditions.

[0021] FIG. 14 is a graph showing the Shore D hardness of cured Example X as a function of time (days) and cured by laser, oven, or ambient conditions.

[0022] FIG. 15 is a graph showing the Shore D hardness of cured Example Y as a function of time (days) and cured by laser, oven, or ambient conditions.

[0023] FIG. 16 is a graph showing the Shore D hardness of cured Example Z as a function of time (days) and cured by laser, oven, or ambient conditions.DETAILED DESCRIPTION

[0024] 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.

[0025] As described in more detail below, the composition may comprise (a) an epoxycontaining compound and (b) a thiol-containing compound and / or an amine-containing compound.Electromagnetic Radiation and Laser

[0026] 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.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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.

[0033] 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.

[0034] 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.

[0035] 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.

[0036] 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.

[0037] 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).

[0038] 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.

[0039] 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.

[0040] 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.

[0041] 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.

[0042] 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.

[0043] 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 Jim to 200 Jim 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.

[0044] 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 pm to 600 pm or larger.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] 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.

[0049] 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.

[0050] 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.

[0051] EMR may be generated by a robotically guided laser and / or LED.Photothermally Active Material

[0052] 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 3% 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.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] 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 trioxidc; antimony trioxidc; 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.

[0057] The photothermally active material that may be used in the compositions disclosed herein also include calcium carbonate; dolomite; huntite; and / or hydromagnesite.

[0058] 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.

[0059] The photothermally active material that may be used in the compositions disclosed herein also include barium sulfate and / or barium manganate sulfate.

[0060] 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.

[0061] 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.

[0062] The photothermally active material that may be used in the compositions disclosed herein also includes cadmium sulfide; cadmium selenide; and / or cadmium sulfoselenide.

[0063] The photothermally active material that may be used in the compositions disclosed herein also include cobalt stannate; cobalt phosphate; and / or cobalt aluminate.

[0064] 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.

[0065] 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.

[0066] The photothermally active material may also include a micronized rubber compound.

[0067] 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.

[0068] The photothermally active material may comprise carbon black, manganese dioxide, and / or copper phthalocyanine such as a solubilized pigment.

[0069] 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.

[0070] The photothermally active material may be soluble or may be in a particulate form.

[0071] 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).

[0072] 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.

[0073] 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.Epoxy-Containing Compounds

[0074] The compositions disclosed herein comprises an epoxy-containing compound. The epoxy-containing compound may be monofunctional (also referred to herein as a “monoepoxide”), difunctional (also referred to herein as a “diepoxide”), and / or polyfunctional(also referred to herein as a “polyepoxide”). As used herein, the term “monofunctional” means an atom or molecule that is only capable of reacting to form one new bond. As used herein, the term “poly functional” 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.

[0075] The epoxy-containing compound may be a monomer, a small molecule and / or a polymer. As used herein, “small molecule” refers to a molecule that comprises discrete chemical structures, has a molecular’ weight of less than 400 g / mol, and that is not a polymer (i.e., is not composed of repeating units). The molecular weight of a small molecule may be determined by mass spectrometry. Appropriate mass spectrometry methods for various types of small molecules are available in many references, such as Mass Spectrometry: A Textbook (3rdEdition, 2018, edited by Jurgen Gross). As used herein, “polymer” refers to a molecule having repeating units and includes oligomers, homopolymers, and copolymers.

[0076] Suitable monoepoxides that may be used include monoglycidyl ethers of alcohols and phenols, such as phenyl glycidyl ether, n-butyl glycidyl ether, cresyl glycidyl ether, isopropyl glycidyl ether, glycidyl versatate, for example, CARDURA E available from Shell Chemical Co., and / or glycidyl esters of monocarboxylic acids such as glycidyl neodecanoate, Epodil 741 available from Evonik, Epodil 746 available from Evonik, and ERISYS ® GE-7 available from CVC Thermoset Specialties.

[0077] Suitable polyepoxides include polyglycidyl ethers of Bisphenol A, such as Epon® 828 and 1001 epoxy resins, and Bisphenol F diepoxides, such as Epon® 862, which are commercially available from Hexion Specialty Chemicals, Inc. Other suitable polyepoxides include polyglycidyl ethers of polyhydric alcohols, polyglycidyl esters of polycarboxylic acids, polyepoxides that are derived from the epoxidation of an olefinically unsaturated alicyclic compound, polyepoxides that are derived from the epoxidation of an olefinically unsaturated nonaromatic cyclic compound, polyepoxides containing oxyalkylene groups in the epoxy molecule, and epoxy novolac resins. Still other suitable polyepoxides include epoxidized Bisphenol A novolacs, epoxidized phenolic novolacs, epoxidized cresylic novolac, and triglycidyl p-aminophenol bismaleimide. The epoxy-containing compound may also comprise an epoxy-dimer acid adduct. The epoxy-dimer acid adduct may be formed as the reaction product of reactants comprising a diepoxide compound (such as a polyglycidyl ether ofBisphenol A) and a dimer acid (such as a C36 dimer acid). The epoxy-containing compound may also comprise a carboxyl-tcrminatcd butadicnc-acrylonitrilc copolymer modified epoxy- containing compound. The epoxy-containing compound may also comprise epoxidized castor oil. The epoxy-containing compound may also comprise an epoxy-containing acrylic, such as glycidyl methacrylate. The epoxy-containing compound may also comprise an epoxy-containing polymer such as epoxy-containing polyacrylate.

[0078] The epoxy-containing compound may comprise an epoxy-adduct. The composition may comprise one or more epoxy-adducts. As used herein, the term “epoxy- adduct” refers to a reaction product of reactants comprising (i) a first compound that is at least difunctional and comprises at least one epoxide functional group and (ii) a second compound that does not include an epoxide functional group. For example, the epoxy-adduct may comprise the reaction product of reactants comprising: (1) an epoxy compound, a polyol, and an anhydride; (2) an epoxy compound, a polyol, and a diacid; or (3) an epoxy compound, a polyol, an anhydride, and a diacid.

[0079] The epoxy compound used to form the epoxy-adduct may comprise any of the epoxy-containing compounds listed above that may be included in the composition.

[0080] The polyol used to form the epoxy-adduct may include diols, triols, tetraols and higher functional polyols, i.e. compounds comprising five or more hydroxyl groups per molecule. Combinations of such polyols may also be used. The polyols may be based on a polyether chain derived from ethylene glycol, propylene glycol, butylene glycol, hexylene glycol and the like as well as mixtures thereof. The polyol may also be based on a polyester chain derived from ring opening polymerization of caprolactone (referred to as polycaprolactone-based polyols hereinafter). Suitable polyols may also include poly ether polyols, polyurethane polyols, polyurea polyols, acrylic polyols, polyester polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, polycarbonate polyols, polysiloxane polyols, and combinations thereof. Polyamines corresponding to polyols may also be used, and in this case, amides instead of carboxylic esters will be formed with the diacids and anhydrides.

[0081] The polyol may comprise a polycaprolactone-based polyol. The polycaprolactone-based polyols may comprise diols, triols or tetraols terminated with primary hydroxyl groups. Commercially available polycaprolactone-based polyols include those soldunder the trade name Capa™ from Perstorp Group, such as, for example, Capa 2054, Capa 2077A, Capa 2085, Capa 2205, Capa 3031, Capa 3050, Capa 3091 and Capa 4101.

[0082] The polyol may comprise a poly tetrahydrofuran-based polyol. The polytetrahydrofuran-based polyols may comprise diols, triols or tetraols terminated with primary hydroxyl groups. Commercially available poly tetrahydrofuran-based polyols include those sold under the trade name Terathane®, such as Terathane® PTMEG 250 and Terathane® PTMEG 650 which are blends of linear diols in which the hydroxyl groups are separated by repeating tetramethylene ether groups, available from Invista. In addition, polyols based on dimer diols sold under the trade names Pripol®, Solvermol™ and Empol®, available from Cognis Corporation, or bio-based polyols, such as the tetrafunctional polyol Agrol 4.0, available from BioBased Technologies, may also be utilized.

[0083] The anhydride that may be used to form the epoxy-adduct may comprise any suitable acid anhydride known in the ait. For example, the anhydride may comprise hexahydrophthalic anhydride and its derivatives (e.g., methyl hexahydrophthalic anhydride); phthalic anhydride and its derivatives (e.g., methyl phthalic anhydride); maleic anhydride; succinic anhydride; trimellitic anhydride; pyromelletic dianhydride (PMDA); 3,3 ',4,4'- oxydiphthalic dianhydride (ODPA); 3,3',4,4'-benzopherone tetracarboxylic dianhydride (BTDA); and 4,4 '-diphthalic (hexafluoroisopropylidene) anhydride (6FDA).

[0084] The diacid used to form the epoxy-adduct may comprise any suitable diacid known in the art. For example, the diacids may comprise phthalic acid and its derivates (e.g., methyl phthalic acid), hexahydrophthalic acid and its derivatives (e.g., methyl hexahydrophthalic acid), maleic acid, succinic acid, adipic acid, and the like.

[0085] The epoxy-adduct may comprise a diol, a monoanhydride or a diacid, and a diepoxy compound, wherein the mole ratio of diol, monoanhydride (or diacid), and diepoxy compounds in the epoxy-adduct may vary from 0.5:0.8:1.0 to 0.5:1.0:6.0.

[0086] The epoxy-adduct may comprise a triol, a monoanhydride or a diacid, and a diepoxy compound, wherein the mole ratio of triol, monoanhydride (or diacid), and diepoxy compounds in the epoxy-adduct may vary from 0.5:0.8:1.0 to 0.5:1.0:6.0.

[0087] The epoxy-adduct may comprise a tetraol, a monoanhydride or a diacid, and a diepoxy compound, wherein the mole ratio of tetraol, monoanhydride (or diacid), and diepoxy compounds in the epoxy-adduct may vary from 0.5:0.8:1.0 to 0.5:1.0:6.0.

[0088] The epoxy-containing compound may have at least one functional group in addition to the epoxide functional group(s).

[0089] The epoxy-containing compound may have an epoxy equivalent weight of at least 90 g / eq, such as at least 140 g / eq, such as at least 188 g / eq, and may have an epoxy equivalent weight of no more than 2,000 g / eq, such as no more than 1,000 g / eq, such as no more than 500 g / eq. The epoxy-containing compound may have an epoxy equivalent weight of 90 g / eq to 2,000 g / eq, such as 140 g / eq to 1,000 g / eq, such as 188 g / eq to 500 g / eq. As used herein, “epoxy equivalent weight” is determined by dividing the measured Mw of an epoxy-containing compound by the average number of epoxide functional groups present in the epoxy-containing compound. As used herein, “Mw” refers to the weight average molecular weight measured by gel permeation chromatography using a separation module and polystyrene standards and tetrahydrofuran (THF) as the eluent.

[0090] The composition may comprise the epoxy-containing compound in an amount of at least 1% by weight based on total solids weight of the composition, such as at least 3% by weight, such as at least 5% by weight. The composition may comprise the epoxy-containing compound in an amount of no more than 95% by weight based on total solids weight of the composition, such as no more than 90% by weight, such as no more than 85% by weight. The composition may comprise the epoxy-containing compound in an amount of 1% by weight to 95% by weight based on total solids weight of the composition, such as 3% by weight to 90% by weight, such as 5% by weight to 85% by weight.Amine-Containing Compound

[0091] The composition may further comprise an amine-containing compound. The amine-containing compound may be blocked, unblocked, encapsulated, or unencapsulated. Suitable amines for use in the composition disclosed herein can be selected from a wide variety of known amines such as primary amines and / or secondary amines.

[0092] The amine-containing compound may include monoamines or polyamines having at least two functional groups such as di-, tri-, and / or higher functional amines. The amine may be aromatic and / or aliphatic, such as cycloaliphatic. Non-limiting examples of suitable amines may include aliphatic polyamines such as but not limited to ethylamine, isomeric propylamines, butylamines, pentylamines, hexylamines, cyclohexylamine, ethylene diamine, 1,2- diaminopropane, 1,4-diaminobutane, 1,3-diaminopentane, 1 ,6-diaminohexane, 2-methyl-l,5-pentane diamine, 2,5-diamino-2,5-dimethylhexane, 2,2,4- and / or 2,4,4-trimethyl-l ,6-diamino- hcxanc, 1,11-diaminoundccanc, 1,12-diaminododccanc, 1,3- and / or 1 ,4-cyclohcxanc diamine, 1- amino-3,3,5-trimethyl-5-aminomethyl-cyclohexane, 2,4- and / or 2,6-hexahydrotoluoylene diamine, 2,4'- and / or 4,4'-diamino-dicyclohexyl methane and 3,3'-dialkyl-4,4'-diamino- dicyclohexyl methanes (such as 3,3'-dimethyl-4,4'-diamino-dicyclohexyl methane and 3,3'- diethyl-4,4'-diamino-dicyclohexyl methane), 2,4- and / or 2,6-diaminotoluene and 2,4'- and / or 4,4 '-diaminodiphenyl methane, piperazines or adducts or derivatives thereof, or mixtures thereof.

[0093] Non-limiting examples of suitable secondary amines can include mono- and polyacrylate and methacrylate modified amines; poly aspartic 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.

[0094] The amine-containing compound may comprise an amine-functional resin.Suitable amine-functional resins can be selected from a wide variety known in the art and can include those having 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 may have a mole ratio of amine-functionality to the ester of no more than 1 : 1 so that no excess primary amine remains upon reaction. A non-limiting example of such polyaspartic esters may include the derivative of diethyl maleate and l,5-diamino-2- methylpentane, which is available commercially from Covestro under the trade nameDesmophen 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.

[0095] The amine may include a high molecular weight primary amine, such as but not limited to a polyoxyalkyleneamine. Suitable polyoxyalkyleneamines may contain two or more primary amino groups attached to a backbone derived, for example, from propylene oxide and / or ethylene oxide. Non-limiting examples of such amines may include those available under the designation JEFF AMINE from Huntsman Corporation. Such amines may have a numberaverage 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.

[0096] The amine may comprise an alkanolamine. As used herein, the term “alkanolamine” refers to a compound comprising a nitrogen atom bonded to at least one alkanol substituent comprising an alkyl group comprising a primary, secondary or tertiary hydroxyl group. The alkanolamine may have the general structure R1nN(R2-OH)3-n, wherein R1comprises hydrogen or an alkyl group, R2comprises an alkanediyl group, and n = 0, 1 or 2. When n = 2, two R1groups will be present, and these groups may be the same or different. When n = 0 or 1, 2 or 3 R2-OH groups will be present, and these groups may be the same or different. The alkyl groups comprise aliphatic linear or branched carbon chains that may be unsubstituted or substituted with, for example, ether groups. Suitable alkanolamines include monoalkanolamines such as ethanolamine, 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.

[0097] The composition may comprise the amine in an amount of at least 1% by weight based on total solids weight of the composition, such as at least 3% by weight, such as at least 5% by weight. The composition may comprise the amine in an amount of no more than 95% by weight based on total solids weight of the composition, such as no more than 90% by weight, such as no more than 85% by weight. The composition may comprise the amine in an amount of 1% by weight to 95% by weight based on total solids weight of the composition, such as 3% by weight to 90% by weight, such as 5% by weight to 85% by weight.Thiol-Containing Compound

[0098] The composition may comprise a thiol-containing compound. The thiol- containing compound 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.

[0099] The thiol-containing compound 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.

[0100] 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.

[0101] The polythiol compound may comprise a dithiol compound, such as 3,6-dioxa- 1,8-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, l,3-dithio-3-methylbutane, ethylcyclohexyldithiol (ECHDT), methylcyclohexyldithiol, methyl-substituted dimercaptodiethyl sulfide, dimethyl-substituted 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). The polythiol 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). 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.

[0102] 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, — [( — CH2)P— X]q— ( — CH2)r; or — [( — CH2)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-C6alkyl and R2is C2-Ce alkyl.

[0103] Polythioethers according to the present disclosure may have the formula IT:orB— { R8— S— R1— [— S— CH2CH2— O— (R2— O)m— CH2— S— R1]n— SH }zwherein 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.

[0104] Other suitable polythioethers for use in the compositions of the present disclosure include, for example, mercapto-propionates, mercapto-acetates, and / or mercapto-acrylates.

[0105] 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 (TEMPTC), di-pentaerythritol hexa(3- mercaptopropionate) (di-PETMP), tri(3-mercaptopropionate) pentaerythritol, and / or triethylolethane tri-(3-mercaptopropionate) .

[0106] 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.

[0107] 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.

[0108] The thiol-containing 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 thiol equivalent 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 / eq, such as no more than 1 ,650 g / eq. 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.

[0109] The composition may comprise the thiol in an amount of at least 1% by weight based on total solids weight of the composition, such as at least 3% by weight, such as at least 5% by weight. The composition may comprise the thiol in an amount of no more than 95% by weight based on total solids weight of the composition, such as no more than 90% by weight, such as no more than 85% by weight. The composition may comprise the thiol in an amount of 1% by weight to 95% by weight based on total solids weight of the composition, such as 3% by weight to 90% by weight, such as 5% by weight to 85% by weight.Accelerator

[0110] The compositions disclosed herein optionally may comprise an accelerator. As used herein, the term “accelerator” means a substance that increases the rate or decreases the activation energy of a chemical reaction in comparison to the same reaction in the absence of the accelerator. An accelerator may be either a “catalyst,” that is, without itself undergoing any permanent chemical change, or may be reactive, that is, capable of chemical reactions and includes any level of reaction from partial to complete reaction of a reactant.

[0111] The accelerator may be latent, blocked, and / or encapsulated. As used herein, the terms “latent” or “blocked” or “encapsulated”, when used with respect to a nucleophile or anaccelerator, means a molecule or a compound that is activated by an external energy source prior to reacting (i.c., crosslinking) or having a catalytic effect, as the case may be. For example, an accelerator may be in the form of a solid at room temperature and have no catalytic effect until it is heated and melts, or the latent accelerator may be reversibly reacted with a second compound that prevents any catalytic effect until the reversible reaction is reversed by the application of heat and the second compound is removed, freeing the accelerator to catalyze reactions.

[0112] The latent accelerator may comprise a reaction product of reactants comprising (i) an epoxy compound, and (ii) an amine and / or an alkaloid. For example, the heat-activated latent accelerator may comprise a reaction product of reactants comprising (i) an epoxy compound and (ii) an amine, or a reaction product of reactants comprising (i) an epoxy compound and (ii) an alkaloid. Such heat-activated latent molecules are described in paragraphs

[0098] through

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

[0113] Other suitable accelerators that may be used include guanidines, substituted guanidines, substituted ureas, melamine resins, guanamine derivatives, heat-activated cyclic tertiary amines, and / or aromatic amines. Examples of substituted guanidines are methylguanidine, dimethylguanidine, trimethylguanidine, tetramethylguanidine, methylisobiguanidine, dimethylisobiguanidine, tetramethylisobiguanidine, hexamethylisobiguanidine, heptamethylisobiguanidine, and / or cyanoguanidine (dicyandiamide). Representatives of suitable guanamine derivatives which may be mentioned are alkylated benzoguanamine resins, benzoguanamine resins and / or methoxymethylethoxymethylbenzoguanamine. In addition, catalytically active substituted ureas may also be used. Suitable catalytically-active substituted ureas include p-chlorophenyl-N,N- dimethylurea, 4,4’-methylenebis(phenyldimethyl urea), 1 , 1 -dimethylurea, N-3- (dimcthylamino)carbony laminomcthyl-3.5.5-t imethy Icyclohcxy l- / V. / V-dimethy lurca. [1,1’ -(4-methyl-m-phenylene)bis(3,3-dimethylurea), 3-phenyl- 1 ,1 -dimethylurea (fenuron) or 3,4- dichlorophcnyl-N,N-dimcthylurca (also known as Diuron).

[0114] Additional examples of suitable accelerators include molecules comprising an unblocked nucleophilic functional group, such as pyridine, imidazole, dimethylaminopyridine, 1- methylimidazole, N,N’ -carbonyldiimidazole, [2,2]bipyridine, 2,4,6-tris(dimethylamino methyl)phenol, and / or 3,5-dimethylpyrazole.

[0115] The accelerator may comprise a tertiary amine, a quaternary amine, and / or a Lewis Acid catalyst. The tertiary amine may comprise a cyclic tertiary amine, such as 1,4- diazabicyclo[2.2.2]octane (“DABCO”), l,8-diazabicylo[5.4.0]undec-7-ene (“DBU”), 1,5- diazabicyclo[4.3.0]non-5-ene (“DBN”), and / or l,5,7-triazabicyclo[4.4.0]dec-5-ene (“TBD”). Examples of suitable quaternary amines include tetrabutylammonium bromide, tetrabutylammonium chloride, and / or benzyltrimethylammonium bromide. Examples of suitable Lewis acid accelerators include bismuth (such as K-Kat 348, commercially available from King Industries), zinc (such as K-Kat XK-635 and XK-672, commercially available from King Industries), and / or tin, such as dibutyltin dilaurate (commercially available from Songwon) and / or dibutyltin diacetylacetonate (commercially available from Kaneka).

[0116] The composition may comprise the accelerator in an amount of at least 0.01% by weight based on total solids weight of the composition, such as at least 0.05% by weight, such as at least 0.1% by weight. The composition may comprise the accelerator in an amount of no more than 10% by weight based on total solids weight of the composition, such as no more than 8% by weight, such as no more than 5% by weight. The composition may comprise the accelerator in an amount of 0.01% by weight to 10% by weight based on total solids weight of the composition, such as 0.05% by weight to 8% by weight, such as 0.1% by weight to 5% by weight.Additives, Fillers, and Solvent

[0117] The composition disclosed herein optionally may comprise an additive. Such additives include a rheology modifier, a reactive diluent, a non-reactive diluent, a dispersant, a tackifier, a thermoplastic polymer, a surface-active agent, a flame retardant, a corrosion inhibitor, a UV stabilizer, a hindered amine light stabilizer (HALS), a colorant, a tint, a plasticizer, an adhesion promoter, an antioxidant, a silane, a silane terminated polymer, a silyl terminated polymer, and / or a moisture scavenger.

[0118] As used herein, the term “reactive diluent” refers to a non-volatile molecule or a compound that is used to lower the viscosity of a resin and / or a composition but that has at least one functional group capable of reacting with a functional group(s) on molecules or compounds in the resin or composition.

[0119] As used herein, the term “non-reactive diluent” refers to a non-volatile molecule or a compound that is used to lower the viscosity of a resin and / or a composition but that does not have a functional group capable of reacting with a functional group(s) on molecules or compounds in the resin or composition.

[0120] 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.

[0121] Additive(s), if present at all, may be present in the composition in a combined amount of at least 0.01% by weight based on total solids weight of the composition, such as at least 0.05% by weight, such as at least 0.1% by weight. Additive(s), if present at all, may be present in the composition in a combined amount of no more than 15% by weight based on total solids weight of the composition, such as no more than 10% by weight, such as no more than 5% by weight. Additive(s), if present at all, may be present in the composition in an amount of 0.01% by weight to 15% by weight based on total solids weight of the composition, such as 0.05% by weight to 10% by weight, such as 0.1% by weight to 5% by weight.

[0122] The composition disclosed herein optionally may comprise a filler. Suitable examples of filler useful in the composition include aluminum hydroxide, mica, wollastonite, calcium carbonate, glass microspheres, clay, or combinations thereof.

[0123] The composition may comprise the filler in an amount of at least 0.1% by weight based on total solids weight of the composition, such as at least 1% by weight. The composition may comprise the filler in an amount of no more than 90% by weight based on total solids weight of the composition, such as no more than 80% by weight. The composition may comprise the filler in an amount of 0.1% by weight to 90% by weight based on total solids weight of the composition, such as 1% by weight to 80% by weight.

[0124] The composition disclosed herein may optionally comprise a solvent. As used herein, the term “solvent” refers to a molecule or a compound that is used to lower the viscosityof the resin, volatilizes under ambient conditions, and does not have a reactive functional group capable of reacting with molecules or compounds in a composition.

[0125] The composition can include a solvent, such as an organic solvent and / or water. As used herein, the term “organic solvent” refers to carbon-based substances capable of dissolving or dispersing other substances.

[0126] Suitable organic solvents that can be included in the solvent include, but are not limited to ester, ketone, glycol ether, alcohol, hydrocarbon or mixtures thereof. Suitable ester solvents can include alkyl acetates such as ethyl acetate, n-butyl acetate, n-hexyl acetate, and mixtures thereof. Suitable ketone solvents may include methyl ethyl ketone, methyl isobutyl ketone, and mixtures thereof. Suitable hydrocarbon solvents may include toluene, xylene, aromatic hydrocarbons, and aliphatic hydrocarbons such as hexane, heptanes, and nonane.

[0127] The composition may comprise the solvent in an amount of at least 5% by weight based on total weight of the composition, such as at least 10% by weight, such as at least 20% by weight. The composition may comprise the solvent in an amount of no more than 80% by weight based on total weight of the composition, such as no more than 60% by weight, such as no more than 40% by weight. The composition may comprise the solvent in an amount of 5% by weight to 80% by weight based on total weight of the composition, such as 10% by weight to 60% by weight, such as 20% by weight to 40% by weight.Compositions

[0128] 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.

[0129] The composition may have a total solids content of at least 20% by weight based on total weight of the composition, such as at least 40% by weight, such as at least 60% by weight, such as at least 80% by weight, and may have a total solids content of 100% by weight based on total weight of the composition. The composition may have a total solids content of 20% by weight to 100% by weight based on total weight of the composition, such as 40% by weight to 100% by weight, such as 60% by weight to 100% by weight, such as 80% by weight to 100% by weight.

[0130] The composition may be substantially free, essentially free, or completely free of a photopolymerizable initiator.

[0131] 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.

[0132] The composition may be formulated as a one-component composition, a two- component composition, or a higher-component composition.

[0133] 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. A one- component composition may cure upon exposure to EMR and / or may react at an accelerated rate upon exposure to EMR compared to a reaction rate in the absence of EMR. In the absence of such exposure, the composition will remain largely uncured.

[0134] As used herein, the term “two-component” or “2K” refers to a composition in which the reactive components readily associate to form an interaction or react to form a bond (physically or chemically), i.e., cure, without activation from an external energy source, such as at ambient or slightly thermal conditions, when mixed. One of skill in the art understands that the two components of the composition are stored separately from each other and mixed just prior to application of the composition. A two-component composition may be exposed to EMR as described herein. As used herein, “reactive components” refer to components of the final composition containing reactive functional groups.

[0135] The compositions disclosed herein may be formulated as a IK composition comprising, consisting essentially of, or consisting of (i) an epoxy-containing compound and (ii) an amine and / or a thiol, and (iii) optionally a photothermally active material, an accelerator, an additive, a solvent, and / or a filler.

[0136] 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 epoxy-containing compound; and a second component comprising, consisting essentially of, or consisting of an amine and / or a thiol. The first component and / or the second component may optionally further comprise a photothermally active material, an accelerator, an additive, a filler, and / or a solvent. The first and second components may be mixed immediately prior to use.

[0137] 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.

[0138] The compositions of a two-component composition may be mixed and provided as pre-mixed frozen compositions (PMF). PMFs may be packaged, for example, in a cartridge, a cartridge and plunger, a syringe, or may be supplied as a tape, a cap, or any preformed geometry. PMFs may be cured by external factors, such as EMR. In examples, the PMF may be stored at temperatures of -100°C to -15°C, such as -100°C to -25°C, such as -100°C to -40°C, such as - 75°C to -15°C, such as -75°C to -25°C, such as -75°C to -40°C, to inhibit curing. When applying the composition to the substrate, the composition may be exposed to EMR to initiate cure of the composition. As used herein, the term “inhibit,” when used with respect to curing, refers to restraining, impeding, slowing or interfering with a particular reaction or function. This can be accomplished in a number of ways, for example, controlling the environment to which the composition is exposed, such as limiting the composition’s exposure to ambient conditions.Dispensing Technologies

[0139] Those skilled in the art are aware that dispensing gun technologies include but are not limited to manual, pneumatic, battery powered, automated meter mix and others. Cartridge based systems exist in a variety of configurations which vary the number of cartridges, cartridge sizes, mix tips, dwell time, mix ratios and other properties based on requirements. The sealant may also be packaged into a Semkit® assembly such as those available from PPG Industries, Inc.

[0140] Also disclosed herein is a coating application kit. The compositions disclosed herein may be packaged in a cartridge assembly used for mixing the various components (i.e., the first, the second, etc., components) of the composition. The cartridge assemblies may be configured to hold a two-component composition. The two-component composition may be any of the compositions described above. For example, one of the first component or the second component may comprise a thiol-containing component, and the other of the first component and the second component may comprise an oxidant.

[0141] The cartridge assembly may comprise a cartridge and an injector. The cartridge may contain the first component of the composition. The injector may contain the secondcomponent of the composition. The cartridge and the injector may be structured and arranged to allow the second component to flow into the cartridge to form a composition.

[0142] The cartridge assembly may comprise a cartridge comprising a first compartment containing the first component of the composition, a second compartment containing the second component of the composition, and a barrier separating the first compartment and the second compartment. A piercer may be structured and arranged to break the barrier to allow the first component and the second component to flow together to form a composition.

[0143] The kit further comprises instructions for exposing the composition to EMR generated by a laser and / or an LED to cure the composition, as described herein.Methods and Cured Coatings

[0144] Disclosed herein are methods of curing any of the compositions described above.

[0145] The composition may be applied alone or as part of a system that can be deposited in a number of different ways onto a number of different substrates. Accordingly, disclosed herein are methods for treating a substrate comprising, consisting essentially of, or consisting of contacting a surface of the substrate with any of the compositions disclosed herein and exposing the composition to an EMR generated by a laser and / or an LED as described above. The composition may be applied to the surface of the substrate in any number of different ways by depositing, applying, or contacting the composition to the substate surface to form a coating thereon, non-limiting examples of which include extruding, pressing, grouting, caulking, spreading, brushing, rolling, troweling, dipping, spraying, and the like.

[0146] In some instances, the composition may be packaged in various dispensing devices known to those skilled in the art, such as a cartridge assembly (as described above) used for mixing the various components (i.e., the first, the second, etc. components) of the composition. Once discharged from the coating application kit, the composition may be applied to a substrate surface using any of the methods described above and may be cured as described herein.

[0147] Compositions may be applied in different environments such as a spray booth, a hangar, a production line, a paint shop, an open workspace, or a clean room based on the need to protect the composition from airborne contaminants. Spray booths can be maintained to keep constant temperature and humidity. Enclosures may be used in hangar operations to help with cleanliness. Ventilation can aid in removing airborne particles, fumes, and overspray whilemaintaining optimal temperature and humidity conditions. Negative pressure systems or HEPA filters may be used to assist in contaminant removal. Coating repair or application may take place in remote locations lacking booths, hangars, or portable enclosures.

[0148] 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.

[0149] The methods may comprise exposing the compositions comprising the epoxycontaining compound and the thiol-containing compound and / or the amine-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 10 minutes to cure the composition. The methods may comprise exposing the compositions comprising the epoxy-containing compound and the thiol-containing compound and / or the amine-containing compound to EMR with a ramp from ambient to a temperature setpoint of at least 70°C, such as at least 90°C, such as at least 110°C and then held at the temperature setpoint of at least at least 70°C, such as at least 90°C, such as at least 110°C for at least 10 minutes to cure the composition. The methods may comprise exposing the compositions comprising the epoxy-containing compound and the thiol- containing compound and / or the amine-containing compound to EMR with a ramp from ambient to a temperature setpoint of at least 60°C and then held at the temperature setpoint of at least 60°C for at least 5 minutes to cure the composition.

[0150] The methods may comprise exposing the compositions to EMR at an intensity of at least 0.01 W / cm2, such as at least 0.1 W / cm2, such as at least 0.2 W / cm2. The methods may comprise exposing the compositions to EMR at an intensity of no more than 108W / cm2, such as no more than 106W / cm2, such as no more than 104W / cm2, such as no more than 102W / cm2, such as no more than 15 W / cm2, such as no more than 12 W / cm2. The methods may comprise exposing the compositions to EMR at an intensity of 0.01 W / cm2to 108W / cm2, such as 0.1 W / cm2to 106W / cm2, such as 0.1 W / cm2to 104W / cm2, such as 0.1 W / cm2to 102W / cm2, such as 0.1 W / cm2to 15 W / cm2, such as 0.2 W / cm2to 12 W / cm2.

[0151] The composition may be cured as described herein to form a coating, such as a sealant, an adhesive, a gap filler, a pottant, a prepreg, and / or a liquid shim.

[0152] 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.

[0153] The methods disclosed herein may further comprise coating the substrate surface with a second 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.

[0154] 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 to the applying.

[0155] 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.

[0156] 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.

[0157] 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.

[0158] 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.

[0159] The methods disclosed herein may be performed using a robotically guided laser and / or LED.

[0160] The methods disclosed herein may include “flashing” or a “dwell time” prior to exposing the compositions to EMR, such as to remove volatile components from the composition, such as solvents, including organic solvents and / or water, or to allow for flow and leveling. The flash or dwell time may be at ambient or elevated temperature 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 which solvents begin to evaporate. As used herein, “dwell time” refers to an amount of time a composition is in contact with a substrate surface prior to further processing or drying.

[0161] 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 not be heated above 120 C, such as not above 100°C, such as not above 80°C, such as not above 60°C, such as not above 40°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 - that is, substrates that cannot withstand the heat at which compositions are conventionally cured, such as at least 60°C, such as at least 80°C, such as at least 110°C, such as at least 120°C.

[0162] The methods may comprise exposing the composition to EMR for at least 5 minutes, such as at least 10 minutes.

[0163] The composition disclosed herein may be applied to a substrate surface and cured as described above to form a coating. Upon exposure of a composition to EMR, the heat generated by the exposure may be localized and sufficient to cure the composition.

[0164] 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.

[0165] 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

[0166] In other examples, it may be advantageous to accelerate cure of the composition to be tack-free on its surface, thereby facilitating productivity by shortening the wait time before a coating may be touched or further processed. “Tackiness” may be evaluated using the fingerprint test, which may consist of touching the composition with a gloved finger following exposure to EMR and assessing the tackiness or stickiness of the formed coating. If the gloved finger does not stick to the coating, then the coating may be called “tack-free” at that time point, and if the gloved finger sticks to the coating, was sticky, and / or left a residue on the glove, then the coating may be called “tacky.” For example, “tackiness” may be evaluated within no more than 336 hours of curing the composition , such as no more than 168 hours, such as no more than 144hours, such as no more than 120 hours, such as no more than 96 hours, such as no more than 72 hours, such as no more than 48 hours, such as no more than 24 hours, such as no more than 12 hours, such as no more than 6 hours, such as no more than 1 hour, such as no more than 30 minutes, such as no more than 10 minutes, such as no more than 5 minutes, such as no more than 4 minutes, such as no more than 3 minutes, such as no more than 1 minute, such as no more than 30 seconds, such as no more than 15 seconds, such as no more than 10 seconds, such as no more than 5 seconds, such as no more than 4 seconds, such as no more than 3 seconds, such as no more than 2 seconds, such as no more than 1 second.

[0167] The methods disclosed herein may comprise a dual cure method wherein the composition is exposed to EMR to achieve a tack-free surface and thereafter the composition may continue to cure through dark cure. The compositions disclosed herein may achieve a tack- free surface as described above following the onset of exposing the composition to the EMR, while the composition may dark cure under ambient conditions to achieve desired physical properties, such as Shore A hardness, within 4 hours, such as within 8 hours, such as within 24 hours, such as within 50 hours, such as within 100 hours, such as within 168 hours, such as within 200 hours, such as within 300 hours, such as within 400 hours, such as within 1,344 hours, such as within 2,688 hours. That is, following exposure of the composition to EMR, complete cure of the coating may be achieved at ambient conditions within at least 400 hours.

[0168] The methods disclosed herein may cure the compositions to make an article or a pre-molded part such as a seal cap, a gasket, an O- ring, a shim, a washer, a grommet, a spacer, a cushion, a mating material, a flange, and / or a plug. As used herein, the term “pre-molded part” refers to a part that has been formed from a composition into a predetermined shape and cured to retain that shape. Although the parts are referred to herein as being “pre-molded”, the parts can be made by any suitable method, such as molding, and the like. The coatings and pre-molded parts made by the methods disclosed herein have the ability, when cured, to resist atmospheric conditions such as moisture and temperature and at least partially block the transmission of materials such as water, water vapor, fuel, solvents, liquids, and / or gases.

[0169] The methods disclosed herein may cure a composition to form a coating and may accelerate cure, while maintaining the performance achieved by coatings formed from the compositions cured at ambient conditions. For example, exposure of the compositions disclosedherein to EMR generated by a laser and / or an LED may cure the composition following exposure to the EMR for a 30 second ramp from ambient to at least 60°C, such as at least 70°C, such as at least 90°C, such as at least 100°C, such as at least 110°C and held at such temperature for at least 5 minutes, such as at least 10 minutes.

[0170] This is demonstrated, for example, by the increase in Shore A hardness measured according to ASTM D2240-15 280 minutes after EMR exposure and / or the increase in Shore D hardness measured according to ASTM D2240-15 20 minutes after EMR exposure.

[0171] 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.

[0172] 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 10 minutes; (ii) held at a temperature setpoint of at least 70°C, such as at least 90°C, such as at least 110°C for at least 10 minutes; and / or (iii) held at a temperature setpoint of at least 60°C for at least 5 minutes. Such methods may result in a coating having similar or improved mechanical properties, such as hairiness, compared to compositions cured under conventional electric oven conditions.

[0173] 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 and maintain the composition at a temperature of 100°C for at least 10 minutes of less than 800 J / cm2, such as less than 750 J / cm2, such as less than 700 I / cm2, such as less than 650 J / cm2, such as less than 600 J / cm2, such as less than 550 J / cm2. It was also surprisingly and unexpectedlydiscovered the total energy density required to ramp and maintain a waterborne compositions disclosed herein comprising a photothcrmally active material at a temperature setpoint of 100°C for at least 10 minutes was reduced by at least 15%, such as by at least 20%, such as by at least 25%, such as by at least 30% 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 10 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 10 minutes, 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.

[0174] 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 and maintain the composition at a temperature of at least 70°C for at least 10 minutes of less than 500 J / cm2, such as less than 450 J / cm2, such as less than 400 J / cm2, such as less than 350 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 at least 70°C for at least 10 minutes was reduced by at least 5%, 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 10 minutes.

[0175] It also 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 held at a temperature setpoint of at least 70°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 hairiness, measured 1 hour following the exposure to the EMR and according to ASTM D2240-15, of at least 15. The methods disclosed herein also may result in acoating having a Shore A hardness, measured 1 day following the exposure to the EMR and according to ASTM D2240-15 of at least 19, such as at least 20, such as at least 25.

[0176] These results surprisingly and unexpectedly demonstrated that exposure of the compositions to EMR generated by a laser and / or an LED may provide cure on demand without negatively impacting dark cure or mechanical properties of the resulting coating. Thus, it was surprisingly and unexpectedly demonstrated that curing the compositions disclosed herein by exposure to EMR generated by a laser and / or an LED may be advantageous to achieve cure on demand, maintained dark cure mechanisms, and an adhesively robust coating. As used herein, “cure on demand” refers to a composition whose cure rate and / or degree of cure, as measured by Shore A hardness, Shore D hardness, or MEK double rubs as a function of time, for example, can be accelerated by exposure of the composition to EMR having a wavelength of 900 nm to 1,080 nm, such as 960 nm to 985 nm, as disclosed herein.Substrates

[0177] Substrates useful for the methods disclosed herein may be selected from a wide variety of substrates and combinations thereof. Non-limiting examples of substrates include vehicles including automotive substrates, industrial substrates, marine substrates and components such as ships, vessels, and on-shore and off-shore installations, storage tanks such as fuel tanks, packaging substrates, pressurized cabins, architectural substrates, aircraft and aerospace components, batteries and battery components, bus bars, metal wires, electrical and aviation equipment, structural joints and rivets, caps, copper or aluminum conductors, nickel conductors, wood flooring and furniture, fasteners, coiled metals, heat exchangers, vents, an extrusion, roofing, walls, wheels, grates, belts, conveyors, grain or seed silos, wire mesh, bolts or nuts, a screen or grid, HVAC equipment such as environmental control systems, frames, tanks, cords, wires, a rail car, furniture, appliances, apparel, a bulkhead, pipes, transformers, toolboxes, grills, medical equipment, doors, windows, a well, cabinets, pylons, electronics and electronic components including housings and circuit boards, glass, sports equipment, including golf balls, large and / or fixed objects such as stadiums, buildings, bridges, containers such as a food and beverage containers, and the like.

[0178] “Vehicle” as used herein refers to in its broadest sense all types of vehicles, such as, but not limited to, cars, trucks, buses, tractors, harvesters, heavy duty equipment, vans, golf carts, motorcycles, bicycles, railcars, subway cars, airplanes, drones, VTOLs, helicopters, ships,vessels, boats of all sizes and the like. A vehicle can include civilian, commercial and military aircraft or land vehicles, such as those listed above and those used in land-based defense (tanks, armored vehicles, and the like). A vehicle can include autonomous and / or unmanned vehicles.

[0179] It will also be appreciated that the substrates of the present disclosure can form a part of a structure. The compositions of the present disclosure can be used in any article of manufacture, such as a vehicle or a structure. “Structure” as used herein refers to a any part of a building, stadium, bridge, transportation infrastructure, oil rig, oil platform, water tower, power line tower, support structures, wind turbines, storage tanks, nuclear plants, walls, piers, docks, levees, dams, shipping containers, trailers, and any metal structure that is exposed to a corrosive environment.

[0180] The substrates, including any of the substrates previously described, can be metallic or non-metallic. Metallic substrates may include both flexible and rigid metal substrates such as tin, iron, steel, and alloys thereof. Non-limiting examples of useful steel materials include cold rolled steel, nickel plated cold rolled steel, hot rolled steel, galvanized (zinc coated) steel, electrogalvanized steel, hot-dipped galvanized steel, galvannealed steel, zinc compounds, zinc alloys, galvalume, steel plated with zinc alloy, stainless steel, cadmium plated steel, pickled steel, zinc-aluminum-magnesium alloy coated steel, aluminum plated steel, aluminum alloy plated steel, steel coated with a zinc-aluminum alloy, or combinations thereof. Metallic substrates may include zinc-aluminum alloys, aluminum, aluminum alloys, magnesium, magnesium alloys, nickel, nickel plating, bronze, tinplate, clad, titanium, brass, copper, silver, gold, 3-D printed metals, cast or forged metals and alloys, or combinations thereof. Aluminum alloys, such as those, for example, of the 1XXX, 2XXX, 3XXX, 4XXX, 5XXX, 6XXX, 7XXX, or 8XXX series as well as clad aluminum alloys and cast aluminum alloys, such as those, for example, of the A356, 1XX.X, 2XX.X, 3XX.X, 4XX.X, 5XX.X, 6XX.X, 7XX.X, or 8XX.X series also may be used as the substrate. The substrate also may comprise, for example, magnesium, such as magnesium alloys of the AZ31B, AZ91C, AM60B, or EV31A series, titanium and / or titanium alloys, such as those of grades 1-36 including H grade variants, copper and copper alloys, or other non-ferrous metals, as well as alloys of these materials.

[0181] Non-metallic substrates include polymeric, plastic, polyester, polyolefin, polyamide, cellulosic, polystyrene, polyacrylic, poly(ethylene naphthalate), polypropylene, polyethylene, nylon, ethylene vinyl alcohol (EVOH), polylactic acid, other “green” polymericsubstrates, poly(ethyleneterephthalate) (PET), polycarbonate, engineering polymers such as poly(cthcrcthcrkctonc) (PEEK), polycarbonate acrylobutadicnc styrene (PC / ABS), polyamide, wood, veneer, wood composite, particle board, medium density fiberboard, cement, stone, glass, paper, cardboard, textiles, leather both synthetic and natural, composite substrates such as fiberglass composites or carbon fiber composites such as fiberglass-epoxy composites or carbon fiber-epoxy composites, 3-D printed polymers and composites, synthetic fibers and the like, such as those available as Kevlar® materials. The shape of the substrate can be in the form of a sheet, plate, bar, rod, or any shape desired.

[0182] The substrate may comprise a bare substrate or the substrate may undergo various treatments prior to application of the composition. For instance, the substrate can be mechanically and / or chemically treated, such as alkaline cleaned, deoxidized, mechanically cleaned and / or abraded, ultrasonically cleaned, solvent wiped, roughened, plasma cleaned or etched, exposed to chemical vapor deposition, treated with an adhesion promoter, plated, anodized, annealed, cladded, or any combination thereof prior to application of the composition. The substrate can be treated using any of the previously described methods prior to application of the composition such as by dipping the substrate in a cleaner and / or deoxidizer bath prior to applying the composition. The substrate can also be plated prior to applying the composition. As used herein, “plating” refers to depositing a metal over a surface of the substrate.Definitions

[0183] For purposes of this detailed description, it is to be understood that the disclosure may assume alternative variations, except where expressly specified to the contrary.

[0184] The numerical values set forth in the examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard variation found in their respective testing measurements.

[0185] 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.

[0186] 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-endedand do not exclude the presence of additional undescribed or unrecited elements, materials, or ingredients. As used herein, “consisting of’ is understood in the context of this application to exclude the presence of any unspecified element, material, or ingredient. As used herein, “consisting essentially of’ is understood in the context of this application to include the specified elements, materials, or ingredients and those that do not materially affect the basic and novel characteristics of what is being described.

[0187] 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.

[0188] As used herein, the terms “on,” “onto,” “applied on,” “applied onto,” “formed on,” “deposited on,” “deposited onto,” and the like mean formed, overlaid, deposited, or provided on, but not necessarily in contact with, a substrate surface. For example, a composition “applied onto” a substrate surface does not preclude the presence of one or more intervening coating layers or films of the same or different composition located between the composition and the substrate surface.

[0189] As used herein, a “composition” refers to a solution, mixture, or dispersion that is capable of forming a coating on a substrate surface. “Coating” as used herein includes films, layers, and the like.

[0190] As used herein, a “sealant composition” refers to a composition that forms a sealant in its cured state.

[0191] As used herein, the term “sealant” refers to a coating that has the ability to resist atmospheric conditions, such as moisture and temperature, and at least partially block the transmission of materials, such as water, fuel, liquids, and gases. The compositions disclosed herein may be useful, for example, as aerospace sealants and linings for fuel tanks.

[0192] As used herein, a “gap filler composition” refers to a composition that forms a gap filler in its cured state.

[0193] As used herein, a “gap filler” refers to a coating that fills a gap between two substrates in order to eliminate air voids, such as filling a crack, a hole, or a butt joint. As used herein, “butt joint” refers to a joint formed by two surfaces abutting at right angles.

[0194] As used herein, an “adhesive composition” refers to a composition that forms an adhesive in its cured state.

[0195] As used herein, an “adhesive” refers to a coating that produces a load-bearing joint.

[0196] As used herein, a “pottant composition” refers to a composition that, when cured, forms a pottant.

[0197] As used herein, a “pottant” refers to an encapsulant.

[0198] As used herein, a “pre-preg” refers to a composition pre-impregnating reinforcement fibers prior to cure.

[0199] As used herein, a “liquid shim composition” refers to a composition that, when cured, forms a liquid shim.

[0200] As used herein, a “liquid shim” refers to a coating that eliminates gaps between substrate surfaces.

[0201] As used herein, “ambient” conditions generally refer to room temperature (e.g., 25 °C) and humidity conditions or temperature and humidity conditions that are typically found in the area in which the composition is applied to a substrate, e.g., at 10°C to 40°C and 5% to 80% relative humidity, while slightly thermal conditions are temperatures that are slightly above ambient temperature, but are generally below the curing temperature for the composition (i.e., in other words, at temperatures and humidity conditions below which the reactive components will readily react and cure, e.g., > 40°C and less than 220°C at 20% to 80% relative humidity).

[0202] As used herein, “total solids” refers to the non-volatile content of the composition, i.e., materials which will not volatilize when heated to 110°C and standard atmospheric pressure (1 atm) for 60 minutes.

[0203] As used herein, the term “cure,” “curing,” and similar terms, mean that the components that form the composition begin to crosslink (i.e., interact and / or react) to form a coating or a bond or a surface that is tack free. In the case of a 2K composition, the composition begins to cure when the components of the composition are mixed, resulting in the reaction of the reactive functional groups of the components of the composition and / or the physical interaction of the components of the composition.

[0204] As used herein, “tack free” means a material that is dry to the touch on the surface and that does not leave a residue when touched (see AS5127 / ID).

[0205] As used herein, a dash (“ — ”) that is not between two letters or symbols is used to indicate a point of bonding for a substituent or between two atoms. For example, — CONH2refers to an amide functional group that is bonded to another chemical moiety through the carbon atom.

[0206] As used herein, “alkoxy” refers to a — OR group where R is alkyl or aromatic as defined herein. Non-limiting examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, and n-butoxy.

[0207] As used herein, “alkyl” refers to an aliphatic hydrocarbon group which may be straight or branched and comprising carbon atoms in a chain. Branched means that one or more alkyl groups such as methyl, ethyl or propyl, are attached to a linear alkyl chain. “Alkyl” may be unsubstituted or optionally substituted by one or more substituents which may be the same or different, each substituent being independently selected from the group consisting of halo, alkyl, aryl, cycloalkyl, cyano, hydroxy, alkoxy, alkylthio, amino, — NH(alkyl), — NH(cycloalkyl), — N(alkyl)2, carboxy and — C(O)O-alkyl. Non-limiting examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl and t-butyl.

[0208] As used herein, unless indicated otherwise, the term “substantially free” means that a particular material is not purposefully added to a mixture or composition, respectively, and is present only as an impurity in a trace amount of less than 0.05% by weight based on a total weight of the mixture or composition, respectively. As used herein, unless indicated otherwise, the term “essentially free” means that a particular material is present only in an amount of less than 0.01% by weight based on a total weight of the mixture or composition, respectively. As used herein, unless indicated otherwise, the term “completely free” means that a mixture or composition, respectively, does not comprise a particular material, i.e., the mixture or composition comprises 0% by weight of such material.

[0209] In view of the foregoing description the present disclosure thus relates in particular to the following Aspects 1 to 128 without being limited thereto.

[0210] 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 epoxy-containing compound and (b) an amine - containing compound and / or a thiol-containing compound.

[0211] 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 epoxy-containing compound and (b) an amine - containing compound and / or a thiol-containing compound.

[0212] Aspect 3. The method of aspect 1 or aspect 2, wherein the EMR comprises visible light and / or near infrared light.

[0213] 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.

[0214] Aspect 5. The method of any of the preceding aspects, wherein the EMR comprises a wavelength of at least 960 nm.

[0215] 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.

[0216] 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.

[0217] 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.

[0218] 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.

[0219] Aspect 10. The method of any of the preceding aspects, wherein the EMR comprises a wavelength of 960 nm to 985 nm.

[0220] 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.

[0221] Aspect 12. The method of any of the preceding aspects, wherein the EMR is directional.

[0222] Aspect 13. The method of any of the preceding aspects, wherein the EMR comprises monochromatic light and / or polychromatic light.

[0223] Aspect 14. The method of any of the preceding aspects, wherein the EMR is coherent.

[0224] Aspect 15. The method of any of aspects 1 and 3 to 14, wherein the laser and / or the LED is defocused.

[0225] Aspect 16. The method of any of the preceding aspects, wherein the laser generates diffuse EMR, divergent EMR, and / or collimated EMR.

[0226] 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.

[0227] 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.

[0228] 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.

[0229] 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.

[0230] 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.

[0231] 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.

[0232] 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.

[0233] 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.

[0234] Aspect 25. The method of aspect 24, wherein the unit comprising the laser and / or the LED further comprises an amplifier, a temperature sensor, and / or an IR sensor.

[0235] Aspect 26. The method of aspect 24, wherein the temperature sensor controls a temperature of the composition, a temperature of a substrate, and / or a ramp rate.

[0236] 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.

[0237] Aspect 28. The method of any of the preceding aspects, wherein (i) the laser and / or the LED is a portable device, a hand-held device and / or a robotically guided device, and / or wherein (ii) the laser is connected to a robotically guided device.

[0238] Aspect 29. The method of any of the preceding aspects, wherein the composition further comprises a photothermally active material.

[0239] Aspect 30. The method of aspect 29, wherein the photothermally active material comprises carbon black, activated manganese dioxide, and / or a solubilized pigment.

[0240] Aspect 31. The method of aspect 29 or aspect 30, wherein the photothermally active material comprises carbon black, activated manganese dioxide, and / or copper phthalocyanine.

[0241] Aspect 32. The method of any of aspects 29 to 31, wherein the photothermally active material is soluble and / or in a particulate form.

[0242] Aspect 33. The method of any of aspects 29 to 32, wherein the photothermally active material is a solid, a liquid, dissolved in an aqueous or organic solvent, a dry powder, dispersed in an aqueous or organic solvent, or dispersed in an organic medium that is nonvolatile such as a plasticizer or a reactive diluent.

[0243] Aspect 34. The method of any of aspects 29 to 33, wherein the composition comprises the photothermally active material in an amount of at least 0.0001 percent by weight based on total solids weight of the composition, such as at least 0.001 percent by weight.

[0244] Aspect 35. The method of any of aspects 29 to 34, 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.

[0245] Aspect 36. The method of any of aspects 29 to 35, 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.

[0246] Aspect 37. The method of any of aspects 29 to 36, 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.

[0247] Aspect 38. The method of any of aspects 29 to 34 or aspect 36, 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.

[0248] Aspect 39. The method of any of aspects 29 to 35, 37 or 38, 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.

[0249] Aspect 40. The method of any of the preceding aspects, wherein the epoxycontaining compound is a monoepoxide, a diepoxide, and / or a polyepoxide.

[0250] Aspect 41. The method of any of the preceding aspects, wherein the epoxycontaining compound is a monomer, a small molecule, and / or a polymer.

[0251] Aspect 42. The method of any of the preceding aspects, wherein the epoxycontaining compound has an epoxy equivalent weight of at least 90 g / eq, such as at least 140 g / eq.

[0252] Aspect 43. The method of any of the preceding aspects, wherein the epoxycontaining compound has an epoxy equivalent weight of at least 188 g / eq.

[0253] Aspect 44. The method of any of aspects 1 to 42, wherein the epoxy-containing compound has an epoxy equivalent weight of no more than 2,000 g / eq, such as no more than 1,000 g / eq.

[0254] Aspect 45. The method of any of aspects 1 to 43, wherein the epoxy-containing compound has an epoxy equivalent weight of no more than 500 g / eq.

[0255] Aspect 46. The method of any of the preceding aspects, wherein the epoxy- containing compound has an epoxy equivalent weight of 90 g / eq to 2,000 g / eq, such as 140 g / eq to 1,000 g / eq.

[0256] Aspect 47. The method of any of aspects 1 to 41, 43, and 45wherein the epoxy- containing compound has an epoxy equivalent weight of 188 g / eq to 500 g / eq.

[0257] Aspect 48. The method of any of the preceding aspects, wherein the composition comprises the epoxy-containing compound in an amount of at least 1 % by weight based on total solids weight of the composition, such as at least 3% by weight.

[0258] Aspect 49. The method of any of the preceding aspects, wherein the composition comprises the epoxy-containing compound in an amount of at least 5% by weight based on total solids weight of the composition.

[0259] Aspect 50. The method of any of the preceding aspects, wherein the composition comprises the epoxy-containing compound in an amount of no more than 95% by weight based on total solids weight of the composition, such as no more than 90% by weight.

[0260] Aspect 51. The method of any of the preceding aspects, wherein the composition comprises the epoxy-containing compound in an amount of no more than 85% by weight based on total solids weight of the composition.

[0261] Aspect 52. The method of any of aspects 1 to 50, wherein the composition comprises the epoxy-containing compound in an amount of 1% by weight to 95% by weight based on total solids weight of the composition, such as 3% by weight to 90% by weight.

[0262] Aspect 53. The method of any of aspects 1 to 47, 49 and 51, wherein the composition comprises the epoxy-containing compound in an amount of 5% by weight to 85% by weight based on total solids weight of the composition.

[0263] Aspect 54. The method of any of the preceding aspects, wherein the amine- containing compound is blocked, unblocked, encapsulated, and / or unencapsulated.

[0264] Aspect 55. The method of any of the preceding aspects, wherein the composition comprises the amine-containing compound in an amount of at least 1% by weight based on total solids weight of the composition, such as at least 3% by weight.

[0265] Aspect 56. The method of any of the preceding aspects, wherein the composition comprises the amine-containing compound in an amount of at least 5% by weight based on total solids weight of the composition.

[0266] Aspect 57. The method of any of the preceding aspects, wherein the composition comprises the amine-containing compound in an amount of no more than 95% by weight based on total solids weight of the composition, such as no more than 90% by weight.

[0267] Aspect 58. The method of any of aspects 1 to 56, wherein the composition comprises the amine-containing compound in an amount of no more than 85% by weight based on total solids weight of the composition.

[0268] Aspect 59. The method of any of aspects 1 to 57, wherein the composition comprises the amine-containing compound in an amount of 1% by weight to 95% by weight based on total solids weight of the composition, such as 3% by weight to 90% by weight.

[0269] Aspect 60. The method of any of aspects 1 to 54, 56, or 58, wherein the composition comprises the amine-containing compound in an amount of 5% by weight to 85% by weight based on total solids weight of the composition.

[0270] Aspect 61. The method of any of the preceding aspects, wherein the thiol- con taining compound comprises a monothiol and / or a poly thiol.

[0271] Aspect 62. The method of any of the preceding aspects, wherein the thiol- containing compound has a thiol equivalent weight of at least 80 g / eq, such as at least 100 g / eq.

[0272] Aspect 63. The method of any of the preceding aspects, wherein the thiol- containing compound has a thiol equivalent weight of at least 125 g / eq, such as at least 400 g / eq.

[0273] Aspect 64. The method of any of the preceding aspects, 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.

[0274] Aspect 65. The method of any of the preceding aspects, 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.

[0275] Aspect 66. The method of any of aspects 1 to 64, 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.

[0276] Aspect 67. The method of any of aspects 1 to 61, 63, 65, or 66, 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.

[0277] Aspect 68. The method of any of the preceding aspects, wherein the composition comprises the thiol in an amount of at least 1% by weight based on total solids weight of the composition, such as at least 3% by weight.

[0278] Aspect 69. The method of any of the preceding aspects, wherein the composition comprises the thiol in an amount of at least 5% by weight based on total solids weight of the composition.

[0279] Aspect 70. The method of any of the preceding aspects, wherein the composition comprises the thiol in an amount of no more than 95% by weight based on total solids weight of the composition, such as no more than 90% by weight.

[0280] Aspect 71. The method of any of the preceding aspects, wherein the composition comprises the thiol in an amount of no more than 85% by weight based on total solids weight of the composition.

[0281] Aspect 72. The method of any of aspects 1 to 70, wherein the composition comprises the thiol in an amount of 1% by weight to 95% by weight based on total solids weight of the composition, such as 3% by weight to 90% by weight.

[0282] Aspect 73. The method of any of the preceding aspects 1 to 67, 69, or 71, wherein the composition comprises the thiol in an amount of 5% by weight to 85% by weight based on total solids weight of the composition.

[0283] Aspect 74. The method of any of the preceding aspects, wherein the composition further comprises an accelerator, an additive, a filler, and / or a solvent.

[0284] Aspect 75. The method of aspect 74, wherein the composition comprises the accelerator in an amount of at least 0.01% by weight based on total solids weight of the composition, such as at least 0.1% by weight.

[0285] Aspect 76. The method of aspect 74 or aspect 75, wherein the composition comprises the accelerator in an amount of no more than 10% by weight based on total solids weight of the composition, such as no more than 5% by weight.

[0286] Aspect 77. The method of any of aspects 74 to 76, wherein the composition comprises the accelerator in an amount of 0.01% by weight to 10% by weight based on total solids weight of the composition, such as 0.1% by weight to 5% by weight.

[0287] Aspect 78. The method of any of aspects 74 to 77, wherein the composition comprises the filler in an amount of at least 0.1% by weight based on total solids weight of the composition, such as at least 1% by weight.

[0288] Aspect 79. The method of any of aspects 74 to 78, wherein the composition comprises the filler in an amount of no more than 90% by weight based on total solids weight of the composition, such as no more than 80% by weight.

[0289] Aspect 80. The method of any of aspects 74 to 79, wherein the composition comprises the filler in an amount of 0.1% by weight to 90% by weight based on total solids weight of the composition, such as 1% by weight to 80% by weight.

[0290] Aspect 81. The method of any of aspects 74 to 80, 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.

[0291] Aspect 82. The method of any of aspects 74 to 81, wherein the composition comprises the additive(s) in a combined amount of at least 0.01 percent by weight based on total solids weight of the composition, such as at least 0.1 percent by weight.

[0292] Aspect 83. The method of any of aspects 74 to 82, wherein the composition comprises the additive(s) in a combined amount of no more than 15 percent by weight based on total solids weight of the composition, such as no more than 5 percent by weight.

[0293] Aspect 84. The method of any of aspects 74 to 83, wherein the composition comprises the additive(s) in a combined amount of 0.01 percent by weight to 15 percent by weight based on total solids weight of the composition, such as 0.1 percent by weight to 5 percent by weight.

[0294] Aspect 85. The method of any of aspects 74 to 84, wherein the composition comprises the solvent in an amount of at least 5% by weight based on total weight of the composition, such as at least 10% by weight.

[0295] Aspect 86. The method of any of aspects 74 to 85, wherein the composition comprises the solvent in an amount of no more than 80% by weight based on total weight of the composition, such as no more than 60% by weight.

[0296] Aspect 87. The method of any of aspects 74 to 86, wherein the composition comprises the solvent in an amount of 5% by weight to 80% by weight based on total weight of the composition, such as 10% by weight to 60% by weight.

[0297] Aspect 88. The method of any of the preceding aspects, wherein the composition is a liquid.

[0298] Aspect 89. The method of any of the preceding aspects, wherein the composition has a total solids content of at least 20 percent by weight based on total solids weight of the composition, such as at least 40 percent by weight.

[0299] Aspect 90. The method of any of the preceding aspects, wherein the composition has a total solids content of at least 60 percent by weight based on total solids weight of the composition, such as at least 80 percent by weight.

[0300] Aspect 91. The method of any of the preceding aspects, wherein the composition has a total solids content of 20 percent by weight to 100 percent by weight based on total solids weight of the composition, such as at least 40 percent by weight to 100 percent by weight.

[0301] Aspect 92. The method of any of the preceding aspects, wherein the composition has a total solids content of 60 percent by weight to 100 percent by weight based on total solids weight of the composition, such as 80 percent by weight to 100 percent by weight.

[0302] Aspect 93. The method of any of aspects 1 to 88, wherein the composition has a total solids content of 100 percent by weight based on total solids weight of the composition.

[0303] Aspect 94. 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.

[0304] Aspect 95. The method of any of the preceding aspects, wherein the composition is formulated as a PMF.

[0305] Aspect 96. 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.

[0306] Aspect 97. 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.

[0307] Aspect 98. 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.

[0308] Aspect 99. 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.

[0309] Aspect 100. 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.

[0310] Aspect 101. 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.

[0311] Aspect 102. The method of any of aspects 1 to 100, wherein the composition is exposed to the EMR at an intensity of no more than 104W / cm2, such as no more than 102W / cm2.

[0312] Aspect 103. The method of any of aspects 1 to 100, 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.

[0313] Aspect 104. The method of any of the preceding aspects, wherein the composition is exposed to the EMR at an intensity of 0.01 W / cm2to 108W / cm2, such as 0.1 W / cm2to 106W / cm2.

[0314] Aspect 105. The method of any of aspects 1 to 99, 102, and 104, 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.

[0315] Aspect 106. The method of any of aspects 1 to 98, 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.

[0316] Aspect 107. The method of any of aspects 97 to 106, comprising cleaning and / or deoxidizing the surface of the substrate, such as solvent-wiping, alkaline cleaning, mechanical cleaning, mechanical abrasion, ultrasonic cleaning, plasma cleaning, and / or plasma etching.

[0317] Aspect 108. The method of any of aspects 97 to 107, comprising coating the surface of the substrate with a second coating composition such as a pretreatment coating composition, an electrodepo sitable coating composition, a primer coating composition, a basecoat coating composition, and / or a topcoat coating composition.

[0318] Aspect 109. The method of any of aspects 97 to 108, comprising applying the composition to a damaged portion of the surface of the substrate.

[0319] Aspect 110. The method of aspect 109, wherein the surface of the substrate comprises a pre-existing coating, and wherein the pre-existing coating is at least partially removed prior to the applying.

[0320] Aspect 111. The method of any of the preceding aspects, wherein a temperature of the composition is maintained at a temperature setpoint, such as at least 60°C, such as at least 100°C.

[0321] Aspect 112. The method of any of aspects 97 to 111, wherein a temperature of the surface of the substrate does not increase upon the exposure to EMR, such as wherein the temperature of the substrate does not exceed 121°C upon exposure to the EMR.

[0322] Aspect 113. The method of any of the preceding aspects, further comprising dark curing the composition.

[0323] Aspect 114. The method of aspect 113, wherein the dark curing is for at least 4 hours, such as at least 24 hours.

[0324] Aspect 115. The method of any of the preceding aspects, further comprising flashing the composition prior to exposure to the EMR.

[0325] Aspect 116. The method of any of the preceding aspects, wherein a rate of the curing is accelerated compared to a rate of curing a composition under ambient conditions and / or electric oven conditions.

[0326] Aspect 117. The method of any of the preceding aspects, wherein a total energy density of less than 800 J / cm2is required to cure the coating, such as less than 750 J / cm2.

[0327] Aspect 118. 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 650 J / cm2.

[0328] Aspect 119. The method of any of the preceding aspects, wherein a total energy density of less than 600 J / cm2is required to cure the coating, such as less than 550 J / cm2.

[0329] Aspect 120. The method of any of aspects 29 to 119, 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 20%.

[0330] Aspect 121. The method of any of aspects 29 to 120, 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%.

[0331] Aspect 122. The method of any of aspects 26 to 121, wherein a temperature of the substrate following exposure to the EMR is below a heat deflection temperature of the substrate.

[0332] Aspect 123. A substrate comprising a coating formed from the composition cured by the method of any of the preceding aspects.

[0333] Aspect 124. The substrate of aspect 123, wherein the coating has a Shore A hardness of at least 15 measured according to ASTM D2240-15 at least 1 hour following termination of the exposure to EMR.

[0334] Aspect 125. The substrate of aspect 123 or aspect 124, wherein the coating has a Shore A hardness of at least 19 measured according to ASTM D2240-15 at least 1 day following termination of the exposure to EMR, such as a Shore A hardness of at least 25.

[0335] Aspect 126. A coating application kit for a 2K composition, the kit comprising:(a) a cartridge assembly comprising:(i) a cartridge comprising a first component of the 2K composition; and(ii) an injector containing a second component of the 2K composition; wherein the cartridge and the injector are structured and arranged to allow the second component to flow into the cartridge to form a composition; and(b) instructions for exposing the composition to defocused electromagnetic radiation (EMR) generated by a laser to cure the composition.

[0336] Aspect 127. A coating application kit for a 2K composition, the kit comprising:(a) a cartridge assembly comprising:(i) a cartridge comprising a first compartment containing a first component of the 2K composition, a second compartment containing a second component of the 2K composition, and a barrier separating the first compartment and the second compartment; and(ii) a piercer structured and arranged to break the barrier to allow the first component and the second component to flow together to form a composition; and (b) instructions for exposing the composition to defocused electromagnetic radiation(EMR) generated by a laser to cure the composition.

[0337] Aspect 128. The kit of aspect 126 or aspect 127, wherein the instructions comprise instructions to perform the method of any of aspects 1 to 122.

[0338] Illustrating the disclosure are the following examples, which, however, are not to be considered as limiting the disclosure to their details.EXAMPLES

[0339] For all laser-exposed samples, the laser unit used was a Compact Heating and Drying SYS-CD system supplied by IPG Photonics® Corporation (Marlborough, MA) 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: Waterborne Epoxy CompositionsTable 1: Waterborne Epoxy Clear Base1Non-ionic surfactant2Epoxy resin, 55% solids in water3Rheology modifier

[0340] The waterborne epoxy clear base was prepared by weighing Components 1 and 2 into a glass jar. Component 3 was added, and then the components were hand mixed by spatulauntil homogenous. Finally, Component 4 was added, and again the components were hand mixed by spatula until homogenous.Table 2: Waterborne Epoxy - Black Base4Dispersant5White barium sulfateTable 3: Waterborne Epoxy - White Base

[0341] The pigmented waterborne epoxy bases in Tables 2 and 3 each were prepared by adding Components 1, 2 and 3 into a glass jar followed by Components 4-7. Grind media (1.1 - 1.3 mm zirconia beads, commercially available from Fox Industries) equaling one-half the mass of Components 1 to 7 was added to the jar to form a mill base. The mill base was then placed in the Lau Disperser DAS 200 (Lau GmbH, Germany) for 120 minutes, resulting in a material with a Hegman gauge particle size of 5-6. The mill base was then strained through a 12 -micron mesh filter. The collected material was weighed, and the remaining Components 8 and 9 were added in an amount calculated based on the percent recovery of the mill base.Table 4: Amine Hardener6Amine resin7Glycol ether solvent

[0342] The amine hardener in Table 4 was prepared by weighing out Component 1 into a glass jar, adding Components 2 and 3, and hand mixing with a spatula until the solution was homogenous.Table 5: Sample Composition

[0343] Each sample as individually prepared by weighing into separate jars; (1) the base(s) and (2) the hardener for each individual sample. The base was then added to the hardener, hand mixed thoroughly with a spatula, transferred back to the base jar, then hand mixed with a spatula again. This process was repeated two additional times to ensure proper mixing of the sample.

[0344] Steel panels were pretreated with B1000 / P99X pretreatment (ACT Test Panels LLC, Hillsdale, MI) then powder coated with PCTA89105 RAL 9010 Pure White (PPG Industries, Inc., Pittsburgh, PA) and were used as the substrate for the examples listed in Table 5. The samples were applied to the substrate using a Byk-Gardner drawdown bar with an 8-mil wet film thickness (targeting 1.5 - 3.0 mil dry film thickness). The samples were flashed for 10 minutes at ambient conditions before being placed in a conventional electric oven at 100°C for 10 minutes.

[0345] Samples for the Compact Heating and Drying Laser Processing System (IPG Photonics, Oxford, MA) (“laser unit”) were mixed and drawn down in identical fashion as samples for the conventional electric oven. After a 10-minute flash at ambient conditions,samples were placed in the laser unit. The temperature was ramped from ambient temperature to 100°C in 30 seconds then held at 100°C for 10 minutes.

[0346] Immediately after cooling the cured coating to ambient temperature, coatings cured in the oven and by laser exposure were tested for degree of cure by double methyl ethyl ketone (“MEK”) rubs. This method was conducted by manually rubbing an MEK soaked paper towel across the surface with uniform pressure across the panel and back, equaling one double mb. Testing was stopped at 100 double rubs or until the coating was broken through to the white surface. If 100 double rubs were achieved, the area that was tested was given a rating ranked as follows:Untouched (0% surface marred)Very Slight Mar (>0% to 25% surface marred)Slight Mar (>25% to 50% surface marred)Mai' (>50% to 75% surface marred)Heavy Mar (>75% to 100% surface marred) Results are outlined in Table 6 below.

[0347] Total Energy Density (J / cm2) was calculated according to Equation I above for samples exposed to the laser unit.Table 6: Results

[0348] The results in Table 6 indicate the effectiveness of carbon black as a photothermally active material in waterborne epoxy coatings. The total energy density used to cure the coatings with carbon black pigment (Example G) was significantly reduced compared to the clear and white coatings (Examples F and H). Even in small amounts or in combination with pigmented bases (Example J), there was a distinct reduction in the energy needed to achieve cure. The laser unit was also able to achieve the same or better curing compared to the conventional oven under the same time and temperature conditions.Example 2: Epoxy-Thiol CompositionsTable 7: Epoxy-Thiol Formulation Examples (grams)8Epoxy component, commercially available from Westlake Chemical (Houston, TX).9Epoxy component, commercially available from Blue Cube Operations LLC (Midland, MI).10Commercially available from Penn Color, Inc. (Doylestown, PA).11A polythioether component commercially available from PPG Industries, Inc.

[0349] The epoxy-thiol formulations shown in Table 7 were prepared as follows.Ingredients were mixed using a Hauschild Speedmix DAC mixer, model 600.1 FVZ. The formulations comprised two pails, the Base Pack and the Hardener Pack. The Base Pack was prepared by combining all the listed Base Pack components in Table 1, in the listed order. The materials were mixed using the DAC mixer for 45 seconds at 1800 rpm prior to and following addition of the filler and photo thermally active material. The mixture was inspected and mixed manually with a spatula to ensure homogeneity. The Hardener Pack was a commerciallyavailable material from PPG Industries, Inc. and was prepared according to technical data sheet (TDS) instructions.

[0350] The Base and Hardener Packs were mixed in the ratios listed in Table 7, then subsequently drawn down at dimensions of 1” x 2.5” x 0.125”, using 1 / 8” shims, for all testing. Shore A hardness samples were drawn down on Teflon substrates. Adhesion samples were drawn down on MEK-cleaned 7075-T6 substrates. Cure of the samples was monitored for 1 week according to ASTM D2240- 15(2021) with a final hardness report-out as shown in Tables 8-11.

[0351] Laser exposed samples. Samples were drawn down on Teflon substrates and exposed to the laser at 70°C, 90°C, or 110°C for 10 minutes with a 30 second ramp. Total Energy Density was calculated according to Equation I above. Shore A hardness was measured according to ASTM D2240- 15(2021) after the coating cooled to ambient temperature.

[0352] Oven exposed samples. Samples were drawn down on Teflon substrates and placed in an oven at 70°C for 10 minutes. Shore A hardness was measured according to ASTM D2240-15 after the coating cooled to ambient temperature.

[0353] Ambient-cured samples. Samples were drawn down on Teflon substrates and placed in an environment-controlled cabinet at 25°C, 50% relative humidity (Thermofisher Forma #3940), then checked for Shore A hardness measured according to ASTM D2240-15 at the times indicated in Table 11.Table 8: Shore A Hardness Cure Profile of Epoxy-Thiol Examples Post Laser ExposureSamples not measured

[0354] The data in Table 8 demonstrate that the total energy density required to heat the compositions containing 1% by weight carbon black (based on total solids) to 90°C and 110°C was lower than that required to heat the same composition that did not contain carbon black. All of the samples began to cure within 4 hours. When heated to 110°C, the compositions containing 1% by weight carbon black (based on total solids) demonstrated a substantial improvement in Shore A hardness at Days 3, 4, and 7 compared to the same compositions that did not contain carbon black. At Day 1, the compositions containing carbon black that were heated to 70°C and 90°C demonstrated higher Shore A hardness in comparison to the same compositions that did not contain carbon black, demonstrating a more rapid cure with inclusion of carbon black in the compositions. By Day 7, all samples demonstrated a Shore A hardness of 15 or greater.Table 9: Shore A Hardness Cure Profile of Epoxy-Thiol Examples Post Laser Exposure (70°C for 10 minutes)^Denotes slightly tacky surface

[0355] The data in Table 9 demonstrate that inclusion of a photothermally active material in the compositions resulted in increased Shore A hardness at Days 1, 3, and 7 compared to compositions that did not contain a photothermally active material. All samples began to cure at Day 0 following exposure to the EMR. Compositions P and Q, containing Astrad IS PCN Blue, had a tack free surface at Day 0 following exposure to EMR.Table 10: Shore A Hardness Cure Profile of Epoxy-Thiol Examples Post Oven Exposure (70°C for 10 minutes)* Denotes tacky surface** Samples not measured

[0356] The data in Table 10 demonstrate cure of Examples K to R when exposed to convention oven conditions. The oven-exposed samples demonstrated low or no cure at Day 0. In contrast, the laser-cured samples (Table 9) demonstrated cure immediately after EMR exposure (Day 0). Samples M to R (laser-cured samples) reached full cure at Day 3. However, the oven-exposed samples had a marked increase in Shore A hardness between Day 3,4 and Day 7, indicating that the oven-exposed samples continued to cure 7 days following oven exposure.Table 11: Shore A Hardness Cure Profile of Epoxy-Thiol Examples Under Ambient Conditions^Denotes slightly tacky surface

[0357] The data in Table 11 demonstrate cure of Examples K to R when exposed to conventional ambient conditions. Notably, the ambient-cured coatings did not begin to cure until Day 1. In contrast, the laser-cured samples (Table 9) demonstrated cure at Day 0.Table 12: Energy Density Data Used to Cure Epoxy-Thiol Examples

[0358] The data in Table 12 demonstrate that inclusion of Astrad IS PCN Blue in the composition resulted in a decreased total energy density required to heat to 70°C compared to the same composition that did not contain a photothermally active material. Additionally, as the amount of Astrad IS PCN increased, the total energy density decreased.Example 3: Epoxy- Amine Formulation ExamplesTable 13: Epoxy- Amine Formulations12Blend of bisphenol F epoxy resin and 100 nm diameter core-shell styrene-butadiene rubber available from Kaneka Corporation.13Fumed silica sur face treated with polydimethylsiloxane commercially available from Evonik.Calculated by dividing total weight of PT active material by total weight of the formulation.

[0359] The epoxy-amine formulations shown in Table 13 were prepared as follows. The individual parts were prepared and mixed using a Speedmix DAC mixer. The formulations were comprised of two parts, the Base Pack and the Hardener Pack. The Base and Hardener Packs were prepared separately by combining all the respective listed components in Table 13, in listed order. After all components were added to each Pack, 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.

[0360] The Base and Hardener Packs were manually mixed in the total values listed in Table 13, then subsequently cast into 1-inch 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 D hardness, measured according to ASTM D2240-15 with data reported as shown in Tables 14-16.

[0361] Laser exposed samples. Samples were exposed to the laser at 60°C for 5 minutes with a 30 second ramp. Shore D hardness was measured after the composition cooled to ambient temperature.

[0362] Oven exposed samples. Samples were cast into 1-inch diameter pucks on aluminum weigh pans and cured at an oven setting at 60°C for 5 minutes. Shore D hardness was measured after the composition cooled to ambient temperature.

[0363] Ambient-cured samples. Samples were cast into 1-inch diameter pucks on aluminum weigh pans and placed in an environment-controlled cabinet at 25 °C with 50%relative humidity (Thermofisher Forma #3940). Shore D hardness was measured 5 minutes after application to the substrate.

[0364] Adhesion samples. 10-mil thick samples were drawn down using a drawdown bar on degreased 2024-T3 Al substrate and allowed to cure for 24 hours. A commercial degreaser, Ultrax™ 98D, was used to remove any contamination from fabrication and processing. Each panel was dipped in 37.8°C degreaser bath for 1 minute, then rinsed in a deionized water bath for an additional minute. The panels were subsequently dried in a 70°C oven for 20 minutes. Post-cure, adhesion testing was done via cross-hatch testing per ASTM D3359-23 (Method A) and rated accordingly.Table 14: Shore D Hardness Cure Profile of Epoxy-Amine Post Laser Exposure* Post-cured samples were foam-like

[0365] The data in Table 14 demonstrate the Shore D hardness (demonstrating cure) of Examples S to Z with laser-exposure. Examples S to U and Y demonstrated cure 20 minutes post-laser exposure. At 180 minutes post-laser exposure, all Examples S to Z demonstrated cure. Notably, Examples S to U and Y foamed upon laser-exposure, which lowered the Shore D hardness values.Table 15: Shore D Hardness Cure Profile of Epoxy- Amine Post Oven Exposure

[0366] The data in Table 15 demonstrate the Shore D hardness (demonstrating cure) of Examples S to Z when exposed to the convection oven. In contrast to the laser-exposed samples (Table 14), none of the oven-exposed samples demonstrated cure until 180 minutes postexposure. The Shore D hardness values 1 day after exposure were comparable between the laser-exposed samples and the oven-exposed samples, except for the samples that foamed (S to U and Y).Table 16: Shore D Hardness Cure Profile of Epoxy-Amine Under Ambient Conditions

[0367] The data in Table 16 demonstrate the Shore D hardness (demonstrating cure) of Examples S to Z when cured at ambient conditions. None of the samples demonstrated any curing at 20 minutes or 60 minutes. Only Sample S demonstrated any curing at 180 minutes,with a Shore D hardness of 2. However, at 1 day, the Shore D hardness of the ambient-cured samples was comparable to both the laser-exposed and oven-exposed samples (except for the laser-cured samples that foamed).

[0368] Overall, the data provided in Tables 14 to 16 demonstrate that curing the compositions contained herein with laser-exposure results in a faster cure than either ovenexposure or ambient cure.Table 17: Material Performance of Epoxy -Amine Examples* Samples were foam-like

[0369] The data in Table 17 demonstrate that Examples S to Z have the same final hardness and adhesion performance (measured according to ASTM D5539) across all three curing conditions (laser-exposed, oven-exposed, and ambient). All samples had an adhesion rating of 5A, which denotes no observed defects after taping. Therefore, as demonstrated in Tables 14 to 16, the laser-cured samples cured faster while maintaining Shore D hardness and adhesion performance.Table 18: Energy Density Data of Epoxy-Amine Examples

[0370] The data in Table 18 show the total energy density during laser cure. As shown, the compositions containing a photothermally active material (Examples S to X and Z) required less energy density to maintain a temperature of 60°C compared to the same composition that does not contain a photothermally active material (Example Y).

[0371] Whereas specific aspects of the disclosure have been described in detail, it will be appreciated by those skilled in the art that various modifications and alternatives to those details could be developed in light of the overall teachings of the disclosure. Accordingly, the particular arrangements disclosed are meant to be illustrative only and not limiting as to the scope of the disclosure which is to be given the full breadth of the claims appended and any and all equivalents thereof.

Claims

We claim:

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

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

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

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

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

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

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

8. The method of claim 7, wherein the photothermally active material comprises carbon black, activated M11O2, and / or copper phthalocyanine.

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

10. The method of any of the preceding claims, wherein a tack-free surface of the coating is achieved at least 1 day following termination of exposure to the EMR.

11. The method of any of the preceding claims, further comprising dark-curing the composition following the exposure to the EMR.

12. The method of claim 11, wherein the dark-curing is for a period of time of at least 4 hours.

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

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

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

17. The substrate of claim 16, wherein the coating has:(a) a Shore D hardness of at least 5 following the exposure to EMR after the coating reached ambient temperature;(b) a Shore A hardness, at least 280 minutes following termination of the exposure to the EMR, of at least 5;(c) a Shore A hardness, at least 4 days following termination of the exposure to EMR, of at least 14;(d) a Shore A hardness, at least 7 days following termination of the exposure to EMR, of at least 14; and / or(e) at least 100 methyl ethyl ketone (“MEK”) double rubs performed according to ASTM D5402-19; wherein the Shore D hardness and the Shore A hardness are measured according to ASTM D2240-15.

18. A coating application kit for a 2K composition, the kit comprising:(a) a cartridge assembly comprising:(i) a cartridge comprising a first component of the 2K composition; and(ii) an injector comprising a second component of the 2K composition; wherein the cartridge and the injector are structured and arranged to allow the second component to flow into the cartridge to form a composition; and(b) instructions for exposing the composition to defocused electromagnetic radiation (EMR) generated by a laser to cure the composition.

19. A coating application kit for a 2K composition, the kit comprising:(a) a cartridge assembly comprising:(i) a cartridge comprising a first compartment containing a first component of 2K the composition, a second compartment containing a second component of the 2K composition, and a barrier separating the first compartment and the second compartment; and(ii) a piercer structured and arranged to break the barrier to allow the first component and the second component to flow together to form a composition; and(b) instructions for exposing the composition to defocused electromagnetic radiation (EMR) generated by a laser to cure the composition.

20. The kit of claim 18 or claim 19, wherein the instructions comprise instructions to perform the method of any of claims 1 to 15.

Images