Methods of curing thermoplastic compositions

Abstract

Disclosed are methods of curing a composition. The method includes exposing the composition to electromagnetic radiation generated by a laser for a period of time sufficient to cure the composition. The composition includes a thermoplastic polymer and optionally also may include a photothermally active material. Also disclosed are substrates comprising a coating formed from a composition cured by the disclosed methods.

Description

METHODS OF CURING THERMOPLASTIC COMPOSITIONSCROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to U.S. Provisional Application No. 63 / 714,541, filed on October 31, 2024, and entitled “Coating Compositions Containing Photothermally Active Materials, Coated Substrates, and Methods of Coating Substrates,” incorporated herein in its entirety.FIELD

[0002] Methods of curing a composition containing a thermoplastic polymer using electromagnetic radiation are disclosed.BACKGROUND

[0003] Multiple industries, including industrial, aerospace, and automotive industries, including the after-market and refinish coating industries, have demonstrated a desire for energy efficient and / or cure-on-demand products.SUMMARY

[0004] Disclosed are methods of curing a composition, comprising exposing the composition to electromagnetic radiation generated by a defocused laser to cure the composition; wherein the composition comprises (a) a thermoplastic polymer and (b) a plasticizer.

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

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

[0007] As described in more detail below, the composition may comprise a thermoplastic polymer and a plasticizer. The composition optionally may further comprise a photothermally active material.Electromagnetic Radiation and Laser

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

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

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

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

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

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

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

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

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

[0017] The laser may be defocused. As used herein, “defocused,” when used with respect to a laser, refers to a manipulation by optics of a light beam generated by the laser 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.

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

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

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

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

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

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

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

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

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

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

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

[0029] A laser and / or an LED may be used to cure coatings over a variety of types of substrate surfaces having a range of surface areas, including a vehicle, such as an automobile, a tractor, a trailer, or an aerospace vehicle, an aerospace structure such as a wing, a skin, and / or a fuselage of an aerospace vehicle, a body in white (that is, the stage before painting in automobile manufacturing in which a car body's frame has been joined together), an appliance or a 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.

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

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

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

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

[0034] Optionally, the composition may comprise a photothermally active material. As used herein, a “photothermally active material” refers to a material whose presence in a composition reduces by at least 5% the total energy density required to ramp and maintain the composition at a temperature setpoint compared to the total energy density required to ramp and maintain the same composition that does not include the material at the temperature setpoint. As used herein, “total energy density” is calculated according to Equation 1:t Zmax%P x LpAX A£Equation 1, where Etot= total energy density in J / cm2; t0= time zero or start of heating cycle; tmax= time to end of heating cycle, wherein the time from t0to 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.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[0050] The photothermally active material may comprise carbon black and / or copper phthalocyanine such as a solubilized pigment.

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

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

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

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

[0055] The compositions may comprise the photothermally active material in an amount of at least 0.0001 percent by weight based on total weight of the composition, such as at least0.01 percent by weight, such as at least 0.1 percent by weight, such as at least 1 percent by weight. The compositions may comprise the photothcrmally active material in an amount of no more than 20 percent by weight based on total 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 weight of the composition, such as 0.01 percent by weight to 15 percent by weight, such as 0.1 percent by weight to 10 percent by weight, such as 1 percent by weight to 10 percent by weight.Thermoplastic Polymers

[0056] As stated above, the composition comprises a thermoplastic polymer and a plasticizer. For example, particles of the thermoplastic polymer may be dispersed in the plasticizer. As used herein, the term “thermoplastic” refers to a component that can be softened or melted when heated and hardened when cooled. For example, a thermoplastic polymer can soften and / or melt upon heating at temperatures greater than 60°C, such as at least 80°C, such as at least 100°C, such as at least 120°C, such as at least 150°C, such as at least 180°C, such at least 200°C, and solidify upon cooling to ambient conditions. Thermoplastic polymers may not need to react with other components of a composition in order to function but that is present as a blended ingredient, i.e., may not form a thermoset material. As used herein, the term “thermoset” refers to a composition that permanently hardens through a reactive process which may become insoluble, infusible, and / or unable to melt at elevated temperatures.

[0057] The thermoplastic polymer may be a homopolymer or a copolymer, such as a block copolymer, and / or a random copolymer. As used herein, the term “block copolymer” refers to a copolymer formed when the two monomers cluster together and form blocks of repeating units. As used herein, the term “random copolymer” refers to a copolymer comprised of more than one kind of repeating unit, in which there is a random distribution of repeating units. The copolymer may be, for example, a terpolymer or a higher-order polymer. As used herein, the term “terpolymer” refers to a polymer that results from copolymerization of three discrete monomers. As used herein, the term “higher-order polymer” refers to a polymer that results from copolymerization of more than three discrete monomers.

[0058] The thermoplastic polymer may be a linear polymer, a grafted polymer, a branched polymer, a brush polymer and / or a star polymer. The thermoplastic polymer may be athermoplastic elastomer. As used herein, a “thermoplastic elastomer” refers to a class of polymers that has both thermoplastic and elastomeric properties, i.e., that can be stretched repeatedly to at least twice their original length at ambient temperature, for example at 23 °C, with an ability to return to their approximate original length when the stress is released.

[0059] The thermoplastic polymer and / or the thermoplastic elastomer optionally may be synthetic or natural. Suitable thermoplastic polymers useful in the present disclosure include polyamides, such as nylon and aramid; polyolefins, such as polybutadiene, polyisobutylene, polybutene, polymethylpentene, amorphous polypropylene, polyethylene terephthalate, polyethylene, polystyrene, ethylene propylene copolymer, polyvinyl chloride, and vinyl chloride copolymer; polyurethanes; styrene block copolymers, such as styrene-butadiene, styrene-isoprene, styrene-butadiene- styrene, styrene-isoprene-styrene, styrene-ethylene / butylene-styrene, styrene-ethylene / propylene, acrylonitrile-butadiene-styrene; polyethers such as polyethylene oxide, polypropylene oxide, polyoxymethylene, poly(p-phenylene ether); ethylene- vinylacetate; polybenzimidazole; polyphenylene sulfide; polyether sulfone; polyether ether ketone; chloroprene; acrylonitrile butadiene; polycarbonate; polyacrylates such as poly(meth)acrylate; or combinations thereof. Examples of useful non-reactive elastomers include Polyvest® polybutadiene available from Evonik. Examples of reactive elastomers include Hypro® ATBN amine-functional butadiene copolymer available from Emerald Performance Materials. Suitable examples of thermoplastic elastomers include olefinic thermoplastic elastomers, polyether block amides polybutadiene thermoplastics elastomer, polyester thermoplastic elastomer, styrenic thermoplastic elastomer, and vinyl thermoplastic elastomers, and rubbers such as butadiene rubber, butyl rubber, bromobutyl rubber, chlorobutyl rubber, polyisobutylene rubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber, ethylene-propylene rubber, fluoroelastomer (vinylidene fluoride-hexafluoropropylene copolymer), natural rubber, neoprene rubber, nitrile rubber, polythioether polysulfide rubber, polyurethane rubber, silicone rubber, and styrene-butadiene rubber.

[0060] The thermoplastic polymer may be dissolved in a carrier liquid such as solvent or water that will be removed for the composition to gel, dry, and / or cure.

[0061] The thermoplastic polymer may be dispersed in a nonvolatile liquid such as a plasticizer that may be stable under ambient and slightly thermal conditions, such as greater than ambient temperature and less than 60°C. Mixtures of thermoplastic polymer in nonvolatile liquidare commonly referred to as plastisols. Upon heating, a cured composition may be formed. Suitable examples include polyvinylchloride (PVC) plastisols.

[0062] The thermoplastic polymer may optionally comprise a reactive functional group that may be reactive at elevated temperatures such as those of at least 60°C, at slightly thermal temperatures, and / or under ambient conditions. Suitable examples of such a reactive functional group include a reactive functional group that is hydrolysable by ambient moisture to react and form crosslinks.

[0063] The thermoplastic polymer may be substantially free or completely free of a reactive functional group. As used herein, the term “reactive functional group” refers to a functional group that is capable of reacting with other functional groups in the composition. As used herein, the term “substantially free” with respect to a reactive functional group on the thermoplastic polymer means that less than one reactive functional group is present on the thermoplastic polymer. As used herein, the term “completely free” with respect to a reactive functional group means that there are 0 reactive functional groups present on the thermoplastic polymer.

[0064] The composition may comprise the thermoplastic polymer in an amount of at least 10 percent by weight based on total weight of the composition, such as at least 20 percent by weight, such as at least 30 percent by weight. The composition may comprise the thermoplastic polymer in an amount of no more than 90 percent by weight based on total weight of the composition, such as no more than 80 percent by weight, such as no more than 60 percent by weight. The composition may comprise the thermoplastic polymer in an amount of 10 by weight to 90 percent by weight based on total weight of the composition, such as 20 percent by weight to 80 percent by weight, such as 30 percent by weight to 60 percent by weight.Plasticizer

[0065] As used herein, the term “plasticizer” refers to a molecule or a compound that does not have a functional group capable of reacting with molecules or compounds in a composition, does not volatilize under ambient conditions, and that is added to the composition to decrease viscosity, decrease glass transition temperature (Tg), impart flexibility, and / or initiate cure of thermoplastic compounds under elevated temperature or slightly elevated temperature.

[0066] Plasticizers that may be used include polymers, trimellitates, sebacates, esters, phthalates, citrates, adipates, benzoates, and the like. Non-limiting examples of such plasticizersinclude diisononylphthalate (Jayflex™ DINP available from Exxon Mobil), dioctylphthalate (Cereplas DOA™ available from Valtris), diisodecylphthalate (Jayflex™ DIDP available from Exxon Mobil), and alkyl benzyl phthalate (Santicizer 278 available from Valtris); benzoate-based plasticizers such as dipropylene glycol dibenzoate (K-Flex® available from Emerald Performance Materials); and other plasticizers including terephthalate-based dioctyl terephthalate (DEHT available from Eastman Chemical Company), alkylsulfonic acid ester of phenol (Mesamoll available from Borchers), epoxidized soybean oil (Plaschek 775 from Valtris), citric acid esters (Citroflex available from Morflex), phenylphophates (Santicizer 148 from Solutia), and 1,2-cyclohexane dicarboxylic acid diisononyl ester (Hexamoll DINCH available from BASF).

[0067] The composition may comprise a plasticizer in an amount of at least 10 percent by weight based on total weight of the composition, such as at least 20 percent by weight, such as at least 30 percent by weight. The composition may comprise a plasticizer in an amount of no more than 90 percent by weight based on total weight of the composition, such as no more than 80 percent by weight, such as no more than 60 percent by weight. The composition may comprise a plasticizer in an amount of 10 percent by weight to 90 percent by weight based on total weight of the composition, such as 20 percent by weight to 80 percent by weight, such as 30 percent by weight to 60 percent by weight.Additional Ingredients

[0068] The compositions disclosed herein optionally may comprise an additive in amounts known to those skilled in the art. Additives may be present in the first component, the second component, and / or a third or higher components. Such additives include a rheology modifier including a thixotrope, a surfactant, a dispersant, a tackifier, a thermoplastic polymer, a surfactant, a flame retardant, a corrosion inhibitor, a UV stabilizer, a colorant, a tint, a solvent, an adhesion promoter, an antioxidant, and / or a moisture scavenger.

[0069] As used herein, the term “solvent” refers to a molecule or a compound that is used to lower the viscosity of a resin, volatilizes under ambient conditions, and does not have a reactive functional group capable of reacting with a functional group(s) on molecules or compounds in a composition.

[0070] Additive(s), if present at all, may be present in the composition in a combined amount of at least 0.1 percent by weight based on total weight of the composition, such as atleast 1 percent by weight. Additive(s), if present at all, may be present in the composition in a combined amount of no more than 20 percent by weight based on total weight of the composition, such as no more than 5 percent by weight. Additive(s), if present at all, may be present in the composition in a combined amount of 0.1 percent by weight to 20 percent by weight based on total weight of the composition, such as 1 percent by weight to 5 percent by weight.

[0071] The compositions disclosed herein 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.

[0072] The skilled person will understand that the selection of accelerator and the amount of such accelerator depends on the exact cure chemistry of the composition and the desired rate of cure, and that the catalyst must be compatible with the other components of the composition. For example, suitable accelerators for the vulcanization of thermoplastic rubber compounds include sulfur-containing compounds such as thiazoles, sulfenamides, thiocarbamates, and thiuram sulfide.

[0073] The composition may be substantially free, essentially free, or completely free of an accelerator. As used herein with respect to the accelerator in the thermoplastic polymer, “substantially free” means that accelerator is present, if at all, in an amount of less than 0.5% by volume based on total volume of the composition. As used herein with respect to the accelerator in the thermoplastic polymer, “essentially free” means that accelerator is present, if at all, in an amount of less than 0.1% by volume based on total volume of the composition. As used herein with respect to the accelerator in the thermoplastic polymer, “completely free” means that accelerator is not present in the composition at all, i.e., there is 0.0% by volume accelerator based on total volume of the composition.

[0074] The compositions disclosed herein may comprise a filler. Useful fillers that may be included in the composition include cellulose, starch, fiberglass, fibrous titanium dioxide, calcium carbonate, carbon fiber (which includes graphite and carbon nanotubes), borosilicate, aluminosilicate, mica, wollastonite, glass microspheres, clay, silicon dioxide, and the like.

[0075] The skilled person will understand that the selection of filler and the amount of such filler depends on various formulation factors including desired loading and must be compatible with the components of the composition.Compositions

[0076] The composition may be substantially free, essentially free, or completely free of a photopolymerizable initiator.

[0077] As used herein, a “IK” or “one-component” composition, is a composition in which all the ingredients may be premixed and stored at ambient conditions and wherein the reactive components do not readily react at ambient or slightly thermal conditions such as greater than ambient temperature and less than 60°C. One-component compositions may cure upon exposure to EMR and / or may cure at an accelerated rate upon exposure to EMR compared to a cure rate in the absence of EMR. In the absence of such exposure, the composition will remain largely uncured.

[0078] The compositions disclosed herein may be formulated as a IK composition comprising, consisting essentially of, or consisting of a thermoplastic polymer and a plasticizer. The IK composition optionally may further comprise a photothermally active material, an additive, an accelerator, and / or a filler as described above.

[0079] The compositions disclosed herein may be formulated, for example, as a composition such as an undercoating composition, a sealant composition, an adhesive composition, an anti-flutter composition, a sound damping composition, a pottant composition, a pre-preg, a liquid shim composition, and / or a gap filler composition.Methods and Cured Coatings

[0080] Disclosed herein are methods of curing any of the compositions described above.

[0081] The compositions may be applied alone or as part of a system that can be deposited in a number of different ways onto a number of different substrates. Accordingly, disclosed herein are methods for treating a substrate comprising, consisting essentially of, or consisting of contacting a surface of the substrate with any of the compositions disclosed herein and exposing the composition to EMR generated by a laser and / or an LED as described above. A coating is typically formed when a composition is deposited onto a substrate surface through manual pressure, mechanical pressure, extrusion, brushing, rolling, spraying (such as airless spraying), and the like.

[0082] Compositions may be applied in different environments such as a spray booth, a hangar, a paint shop, 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. Coating repair or application may take place in remote locations lacking booths, hangars, or portable enclosures.

[0083] 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.

[0084] The methods may comprise exposing the compositions comprising the thermoplastic polymer and the plasticizer to EMR for at least 30 minutes to cure the composition. For example, the method may comprise exposing the composition comprising the thermoplastic polymer and the plasticizer to EMR with a ramp from ambient to a temperature setpoint of at least 140°C and then held at the temperature setpoint of at least 140°C for at least 40 minutes to cure the composition.

[0085] 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.

[0086] 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.

[0087] The coating formed by curing the composition may be, for example, an undercoating, a sealant, an adhesive such as a structural adhesive, an anti-flutter coating, a sounddamper, a pottant, a pre-preg, a liquid shim, or a gap filler. The composition may be cured to form an article, such as by additive manufacturing, such as 3D printing as described below.

[0088] The methods disclosed herein may further comprise coating the substrate surface with a second coating composition in addition to the disclosed composition. 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, 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.

[0089] The methods disclosed herein may comprise applying a composition as described herein to a damaged portion of a substate surface and exposing the composition to EMR generated by a laser and / or an LED as described herein. Optionally, the surface may comprise a pre-existing coating, and the pre-existing coating may be partially removed prior the applying.

[0090] 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.

[0091] 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.

[0092] The methods disclosed herein may include “flashing” or a “dwell time” prior to exposing the composition 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 toevaporate. 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.

[0093] 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.

[0094] 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.

[0095] The methods disclosed herein may be performed using a robotically guided laser and / or LED.

[0096] 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.

[0097] The methods disclosed herein may cure a composition. It was surprisingly discovered that exposure of the compositions 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 140°C for at least 30 minutes. The methods may result in a coating having similar mechanical properties, such as Shore A hardness and adhesion, to compositions cured under conventional oven conditions. For example, the methods disclosed herein may result in a coating having a Shore A hardness, measured after the coating cooling to ambient temperature and at least 30 minutes following the exposure to the EMR and according to ASTM D2240-15, of at least 50, such as a Shore A hardness of at least 55, such as a Shore A hardness of at least 60, such as a Shore A hardness of at least 65, such as a Shore A hardness of at least 70. For example, the methods disclosed herein may result in a coating having a Shore A hardness, measured at least 24 hours after the exposure to the EMR and according to ASTM D2240-15, of at least 55, such as at least60, such as at least 65, such as at least 70, such as at least 75. For example, the methods disclosed herein may result in a coating having cohesive failure similar to that of coatings cured in a conventional oven. That is, the coating was cohesive. As used herein, “cohesive failure” and like terms refer to a coating that, when tested for delamination from the panel, leaves a portion of the coating on the panel (as compared to “adhesive failure,” which refers to a coating that, when tested for delamination from the panel, completely delaminates from the panel).Cohesion and adhesion may be tested using test methods known to those skilled in the art of substrate protection, such as by drawing down composition on a substrate, curing the composition on a surface of the substrate, and using a scraper to manually initiate detachment of the coating, then pulling the coating at a 90° angle relative to the substrate surface.

[0098] As such, laser-exposure did not negatively impact mechanical performance of samples compared to the same composition cured under conventional oven conditions.Additionally, inclusion of photothermally active material in the laser-cured composition did not negatively impact mechanical performance of coatings compared to coatings formed from compositions that did not include the photothermally active material.

[0099] Additionally, 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. For example, when exposed to an EMR having a wavelength of 900 nm to 1,080 nm, such as 960 nm to 985 nm, the total energy density required to ramp and maintain the composition at a temperature of 140°C for at least 30 minutes was less than 3,688 J / cm2, such as less than 3,650 J / cm2, such as less than 3,500 J / cm2, such as less than 3,000 J / cm2, such as less than 2,500 J / cm2, such as less than 2,000 J / cm2, such as less than 1,750 J / cm2.

[0100] It was also surprisingly and unexpectedly discovered the total energy density required to ramp and maintain the compositions disclosed herein at a temperature setpoint of 140°C for at least 30 minutes was reduced by at least 5%, such as by at least 10%, such as by at least 15%, such as by at least 20%, such as by at least 30%, such as by at least 40%, such as by atleast 50%, such as by at least 55% compared to total energy density required to ramp and maintain the same composition that did not include a photothcrmally active material at the temperature setpoint for at least 30 minutes.

[0101] These results surprisingly and unexpectedly demonstrated that exposure of compositions to EMR generated by a laser and / or an LED may provide cure on demand for the disclosed compositions without negatively impacting mechanical properties of the resulting coating. Thus, it was surprisingly and unexpectedly demonstrated that curing the compositions disclosed herein by exposure to EMR generated by a laser and / or an LED may be advantageous to achieve cure on demand and a mechanically robust coating. As used herein, “cure on demand” refers to a composition whose cure rate and / or degree of cure, as measured by Shore A hardness as a function of time, for example, can be accelerated by exposure of the composition to EMR having a wavelength of 900 nm to 1,080 nm, such as 960 nm to 985 nm, as disclosed herein.Substrates

[0102] 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 golfballs, large and / or fixed objects such as stadiums, buildings, bridges, containers such as a food and beverage containers, and the like.

[0103] “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, golfcarts, 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.

[0104] 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.

[0105] 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.

[0106] Non-metallic substrates include polymeric, plastic, polyester, polyolefin, polyamide, cellulosic, polystyrene, polyacrylic, poly(ethylene naphthalate), polypropylene,polyethylene, nylon, ethylene vinyl alcohol (EVOH), polylactic acid, other “green” polymeric substrates, poly(ethyleneterephthalate) (PET), polycarbonate, engineering polymers such as poly(etheretherketone) (PEEK), polycarbonate acrylobutadiene styrene (PC / ABS), polyamide, wood, veneer, wood composite, particle board, medium density fiberboard, cement, stone, glass, paper, cardboard, textiles, leather both synthetic and natural, composite substrates such as fiberglass composites or carbon fiber composites such as fiberglass -epoxy composites or carbon fiber-epoxy composites, 3-D printed polymers and composites, synthetic fibers and the like, such as those available as Kevlar® materials. The shape of the substrate can be in the form of a sheet, plate, bar, rod, or any shape desired.

[0107] 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

[0108] 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.

[0109] 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 its respective testing measurements.

[0110] 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.

[0111] As used herein, “including,” “containing” and like terms are understood in the context of this application to be synonymous with “comprising” and are therefore open-ended and do not exclude the presence of additional undescribed or unrecited elements, materials, or ingredients. As used herein, “consisting of’ is understood in the context of this application to exclude the presence of any unspecified element, ingredient or method step. 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.

[0112] 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.

[0113] 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 other intervening coating layers or films of the same or different composition located between the composition and the substrate surface.

[0114] As used herein, a “composition” refers to a solution, mixture, or a dispersion.

[0115] “Coating” as used herein includes films, layers and the like.

[0116] As used herein, an “undercoating composition” refers to a composition that forms an undercoating in its cured state.

[0117] As used herein, an “undercoating” refers to a coating that is applied after a primer coating and before the topcoat.

[0118] As used herein, an “anti-flutter composition” refers to a composition that forms an anti-flutter coating in its cured state.

[0119] As used herein, an “anti-flutter coating” refers to a coating that prevents contact between two surfaces.

[0120] As used herein, an “sound damper composition” refers to a composition that forms a sound damper in its cured state.

[0121] As used herein, a “sound damper” refers to a coating designed to reduce the transmission of sound by absorbing or dissipating vibrational energy.

[0122] As used herein, a “sealant composition” refers to a composition that forms a sealant in its cured state.

[0123] As used herein, the term “sealant” refers to a coating that has the ability to resist atmospheric conditions, such as moisture and temperature and at least partially block the transmission of materials, such as water, fuel, and other liquid and gasses. The compositions disclosed herein may be useful, for example, as aerospace sealants and linings for fuel tanks.

[0124] As used herein, a “gap filler composition” refers to a composition that forms a gap filler in its cured state.

[0125] 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.

[0126] As used herein, an “adhesive composition” refers to a composition that forms an adhesive in its cured state.

[0127] As used herein, an “adhesive” refers to a coating that produces a load-bearing joint.

[0128] As used herein, a “pottant composition” refers to a composition that, when cured, forms a pottant.

[0129] As used herein, a “pottant” refers to an encapsulant.

[0130] As used herein, a “pre-preg” refers to a composition pre-impregnating reinforcement fibers prior to cure.

[0131] As used herein, a “liquid shim composition” refers to a composition that, when cured, forms a liquid shim.

[0132] As used herein, a “liquid shim” refers to a coating that eliminates gaps between substrate surfaces.

[0133] As used herein, “ambient” conditions generally refer to room temperature (for example, 23 °C) and humidity conditions or temperature and humidity conditions that are typically found in the area in which the composition is applied to a substrate, for example, at 10°C to 40°C and 5% to 80% relative humidity, while “slightly thermal” conditions are temperatures that are 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 composition cure, for example, > 40°C and less than 60°C at 20% to 80% relative humidity).

[0134] As used herein, the term “cure,” “curing,” and similar terms, means that the components that form the composition begin to fuse (i.e., a physical entanglement of the discrete polymer chains) and / or crosslink (i.e., a chemical reaction) to convert the composition from a liquid to a solid state and to form a coating or a bond.

[0135] 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.

[0136] As used herein, a “solid” refers to a material having a viscosity of 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 Is’1.

[0137] As used herein, “polymer” refers to oligomers, homopolymers, and copolymers.

[0138] As used herein, a dash (“ — ”) that is not between two letters or symbols is used to indicate a point of bonding for a substituent or between two atoms. For example, — CONH2 is bonded to another chemical moiety through the carbon atom.

[0139] As used herein, “alkoxy” refers to a — OR group where R is alkyl or aromatic as defined herein.

[0140] As used herein, “alkyl” refers to an aliphatic hydrocarbon group which may be straight or branched and comprising a 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.

[0141] As used herein, the term “(meth) acrylate” refers to either / or methacrylate or acrylate and “(meth)acrylic” refers to either / or methacrylic acid and acrylic acid.

[0142] As used herein, “aromatic,” when referring to a compound, means that the compound comprises at least one aromatic ring.

[0143] As used herein, unless indicated otherwise, the term “substantially free” means that a particular material is not purposefully added to a mixture or composition, respectively, and is only present as an impurity in a trace amount of less than 0.05% by weight based on a totalweight of the mixture or composition, respectively. As used herein, unless indicated otherwise, the term “essentially free” means that a particular material is only present in an amount of less than 0.01% by weight based on a total weight of the mixture or composition, respectively. As used herein, unless indicated otherwise, the term “completely free” means that a mixture or composition, respectively, does not comprise a particular' material, i.e., the mixture or composition comprises 0% by weight of such material.

[0144] In view of the foregoing description the present disclosure thus relates to the following Aspects 1 to 106 without being limited thereto.Aspects

[0145] Aspect 1. A method of curing a composition, comprising:exposing the composition to electromagnetic radiation (EMR) generated by a laser and / or a light emitting diode (LED) to cure the composition; wherein the composition comprises (a) a thermoplastic polymer and (b) a plasticizer.

[0146] Aspect 2. A method of curing a composition, comprising:exposing the composition to electromagnetic radiation (EMR) generated by a defocused laser to cure the composition; wherein the composition comprises (a) a thermoplastic polymer and (b) a plasticizer.

[0147] Aspect 3. The method of aspect 1 or aspect 2, wherein the EMR comprises visible light and / or near infrared light.

[0148] 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.

[0149] Aspect 5. The method of any of the preceding aspects, wherein the EMR comprises a wavelength of at least 960 nm.

[0150] 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.

[0151] 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.

[0152] Aspect 8. The method of any of aspects 1 to 4, 6, and 7, wherein the EMR comprises a wavelength of 300 nm to 2,500 nm, such as 300 nm to 1,500 nm.

[0153] 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.

[0154] Aspect 10. The method of any of the preceding aspects, wherein the EMR comprises a wavelength of 960 nm to 985 nm.

[0155] 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.

[0156] Aspect 12. The method of any of the preceding aspects, wherein the EMR is directional.

[0157] Aspect 13. The method of any of the preceding aspects, wherein the EMR comprises monochromatic light and / or polychromatic light.

[0158] Aspect 14. The method of any of the preceding aspects, wherein the EMR is coherent.

[0159] Aspect 15. The method of any of aspects 1 and 3 to 14, wherein the laser and / or the LED is defocused.

[0160] Aspect 16. The method of any of the preceding aspects, wherein the laser generates diffuse EMR, divergent EMR, and / or collimated EMR.

[0161] 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.

[0162] 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.

[0163] 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.

[0164] 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.

[0165] 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.

[0166] 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.

[0167] 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.

[0168] Aspect 24. The method of any of the preceding aspects, wherein the laser and / or the LED comprises adaptive optics such as optics to tailor focal intensity and / or a wide area distribution of the EMR.

[0169] Aspect 25. The method of any of the preceding aspects, wherein a unit comprising the laser and / or the LED further comprises an amplifier, a temperature sensor, and / or an IR sensor.

[0170] Aspect 26. The method of any of the preceding aspects, wherein the unit comprising the laser and / or the LED further comprises a sensor to control a temperature of the composition temperature, a temperature of a substrate, and / or a ramp rate.

[0171] 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.

[0172] Aspect 28. The method of any of the preceding aspects, wherein the laser and / or the LED comprises a portable device, a hand-held device, and / or a robotically guided device.

[0173] Aspect 29. The method of any of the preceding aspects, wherein the composition further comprises a photothermally active material.

[0174] Aspect 30. The method of aspect 29, wherein the photothermally active material comprises carbon black and / or a solubilized pigment, and / or copper phthalocyanine.

[0175] Aspect 31. The method of aspect 29 or aspect 30, wherein the photothermally active material is soluble and / or in a particulate form.

[0176] Aspect 32. The method of any of aspects 29 to 31, 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.

[0177] Aspect 33. The method of any of aspects 29 to 32, wherein the composition comprises the photothermally active material in an amount of at least 0.0001 percent by weight based on total weight of the composition, such as at least 0.01 percent by weight.

[0178] 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 0.1 percent by weight based on total weight of the composition, such as at least 1 percent by weight.

[0179] Aspect 35. The method of any of aspects 29 to 34, wherein the composition comprises the photothermally active material in an amount of no more than 20 percent by weight based on total weight of the composition, such as no more than 15 percent by weight.

[0180] 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 10 percent by weight.

[0181] Aspect 37. The method of any of aspects 29 to 35, 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 weight of the composition, such as 0.01 percent by weight to 15 percent by weight.

[0182] Aspect 38. The method of any of aspects 29 to 35 and 37, wherein the composition comprises the photothermally active material in an amount of 0.1 percent by weight to 10 percent by weight based on total weight of the composition, such as 1 percent by weight to 10 percent by weight.

[0183] Aspect 39. The method of any of the preceding aspects, wherein the thermoplastic polymer comprises a homopolymer or a copolymer, such as a block copolymer, and / or a random copolymer.

[0184] Aspect 40. The method of any of the preceding aspects, wherein the thermoplastic polymer comprises a linear polymer, a grafted polymer, a branched polymer, a brush polymer and / or a star polymer.

[0185] Aspect 41. The method of any of the preceding aspects, wherein the thermoplastic polymer (i) comprises a thermoplastic elastomer and / or (ii) is synthetic or natural.

[0186] Aspect 42. The method of any of the preceding aspects, wherein the composition further comprises a carrier liquid such as a solvent or water.

[0187] Aspect 43. The method of any of the preceding aspects, wherein the thermoplastic polymer comprises a reactive functional group, such as a reactive functional group that is hydrolysable by ambient moisture to react and form a crosslink.

[0188] Aspect 44. The method of any of the preceding aspects, wherein the thermoplastic polymer is substantially free or completely free of a reactive functional group.

[0189] Aspect 45. The method of any of the preceding aspects, wherein the composition comprises the thermoplastic polymer in an amount of at least 10 percent by weight based on total weight of the composition, such as at least 20 percent by weight.

[0190] Aspect 46. The method of any of the preceding aspects, wherein the composition comprises the thermoplastic polymer in an amount of at least 30 percent by weight based on total weight of the composition.

[0191] Aspect 47. The method of any of the preceding aspects, wherein the composition comprises the thermoplastic polymer in an amount of no more than 90 percent by weight based on total weight of the composition, such as no more than 80 percent by weight.

[0192] Aspect 48. The method of any of the preceding aspects, wherein the composition comprises the thermoplastic polymer in an amount of no more than 60 percent by weight based on total weight of the composition.

[0193] Aspect 49. The method of any of the preceding aspects, wherein the composition comprises the thermoplastic polymer in an amount of 10 percent by weight to 90 percent by weight based on total weight of the composition, such as 20 percent by weight to 80 percent by weight.

[0194] Aspect 50. The method of any of the preceding aspects, wherein the composition comprises the thermoplastic polymer in an amount of 30 percent by weight to 60 percent by weight based on total weight of the composition.

[0195] Aspect 51. The method of any of the preceding aspects, wherein the thermoplastic polymer is in particulate form and is dispersed in the plasticizer.

[0196] Aspect 52. The method of any of the preceding aspects, wherein the composition comprises the plasticizer in an amount of at least 10 percent by weight based on total weight of the composition, such as at least 20 percent by weight.

[0197] Aspect 53. The method of any of the preceding aspects, wherein the composition comprises the plasticizer in an amount of at least 30 percent by weight based on total weight of the composition.

[0198] Aspect 54. The method of any of the preceding aspects, wherein the composition comprises the plasticizer in an amount of no more than 90 percent by weight based on total weight of the composition, such as no more than 80 percent by weight.

[0199] Aspect 55. The method of any of the preceding aspects, wherein the composition comprises the plasticizer in an amount of no more than 60 percent by weight based on total weight of the composition.

[0200] Aspect 56. The method of any of the preceding aspects, wherein the composition comprises the plasticizer in an amount of 10 percent by weight to 90 percent by weight based on total weight of the composition, such as 20 percent by weight to 80 percent by weight.

[0201] Aspect 57. The method of any of the preceding aspects, wherein the composition comprises the plasticizer in an amount of 30 percent by weight to 60 percent by weight based on total weight of the composition.

[0202] Aspect 58. The method of any of the preceding aspects, wherein the composition further comprises an additive, an accelerator, and / or a filler.

[0203] Aspect 59. The method of aspect 58, wherein the additive comprises a rheology modifier including a thixotrope, a surfactant, a dispersant, a tackifier, a thermoplastic polymer, a surfactant, a flame retardant, a corrosion inhibitor, a UV stabilizer, a colorant, a tint, a solvent, an adhesion promoter, an antioxidant, and / or a moisture scavenger.

[0204] Aspect 60. The method of any of the preceding aspects, wherein the composition is substantially free, essentially free, or completely free of an accelerator and / or a photoinitiator.

[0205] Aspect 61. The method of any of aspects 58 to 60, comprising the additive(s) in a combined about of at least 0.1 percent by weight based on total weight of the composition, such as at least 1 percent by weight.

[0206] Aspect 62. The method of any of aspects 58 to 61, comprising the additive(s) in a combined amount of no more than 20 percent by weight based on total weight of the composition, such as no more than 5 percent by weight.

[0207] Aspect 63. The method of any of aspects 58 to 62, comprising the additive(s) in a combined amount of 0.1 percent by weight to 20 percent by weight based on total weight of the composition, such as 1 percent by weight to 5 percent by weight.

[0208] Aspect 64. The method of any of the preceding aspects, wherein the composition is formulated as a 1K composition.

[0209] Aspect 65. The method of any of the preceding aspects, wherein the composition is formulated as an undercoating composition, a sealant composition, an adhesive composition such as a structural adhesive composition, an anti-flutter composition, a sound damping composition, a pottant composition, a pre-preg, a liquid shim composition, and / or a gap filler.

[0210] Aspect 66. The method of any of the preceding aspects, comprising applying the composition to a surface of a substrate, such as by manual pressure, mechanical pressure, and / or extrusion.

[0211] Aspect 67. The method of any of the preceding aspects, wherein the composition is exposed to the EMR for at least 30 minutes.

[0212] Aspect 68. 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.

[0213] Aspect 69. 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.

[0214] Aspect 70. 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.

[0215] Aspect 71. The method of any of the preceding aspects, wherein the composition is exposed to the EMR at an intensity of no more than 104W / cm2, such as no more than 102W / cm2.

[0216] Aspect 72. The method of any of the preceding aspects, wherein the composition is exposed to the EMR at an intensity of no more than 15 W / cm2, such as no more than 12 W / cm2.

[0217] Aspect 73. The method of any of aspects 1 to 68 and 70, 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.

[0218] Aspect 74. The method of any of aspects 1 to 68, 70, 71, and 73, 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.

[0219] Aspect 75. The method of any of aspects 1 to 68 and 70 to 74, 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.

[0220] Aspect 76. The method of any of aspects 66 to 75, 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.

[0221] Aspect 77. The method of any of aspects 66 to 76, the preceding aspects, comprising coating the surface of the substrate with a second coating composition such as a pretreatment composition, an electrodepositable coating composition, a primer coating composition, a basecoat coating composition, and / or a topcoat coating composition.

[0222] Aspect 78. The method of any of the preceding aspects, wherein the substrate comprises a fixed structure.

[0223] Aspect 79. The method of any of aspects 66 to 78, comprising applying the composition to a damaged portion of the surface of the substrate.

[0224] Aspect 80. The method of aspect 79, 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.

[0225] Aspect 81. The method of any of the preceding aspects, wherein a temperature of the composition is maintained at a temperature setpoint, such as at least 140°C.

[0226] Aspect 82. The method of any of aspects 66 to 81, wherein a temperature of the surface of the substrate does not increase upon the exposure to EMR, such as wherein the temperature of the surface of the substrate does not exceed 121°C.

[0227] Aspect 83. The method of any of aspects 66 to 82, further comprising contacting a surface of a second substrate to the composition such that the composition is between the substrate and the second substrate.

[0228] Aspect 84. The method of any of the preceding aspects, further comprising flashing the composition prior to exposure to the EMR.

[0229] Aspect 85. The method of any of the preceding aspects, wherein a total energy density of less than 3,688 J / cm2is required to cure the coating, such as less than 3,650 J / cm2.

[0230] Aspect 86. The method of any of the preceding aspects, wherein a total energy density of less than 3,500 J / cm2is required to cure the coating, such as less than 3,000 J / cm2.

[0231] Aspect 87. The method of any of the preceding aspects, wherein a total energy density of less than 2,500 J / cm2is required to cure the coating, such as less than 2,000 J / cm2.

[0232] Aspect 88. The method of any of the preceding aspects, wherein a total energy density of less than 1,750 J / cm2is required to cure the coating.

[0233] Aspect 89. The method of any of the preceding aspects, wherein a total energy density required to maintain the composition at a temperature of 140°C was less than 3,650 J / cm2, such as less than 3,500 J / cm2.

[0234] Aspect 90. The method of any of the preceding aspects, wherein a total energy density required to maintain the composition at a temperature of 140°C was less than 3,000 J / cm2, such as less than 2,500 J / cm2.

[0235] Aspect 91. The method of any of the preceding aspects, wherein a total energy density required to maintain the composition at a temperature of 140°C was less than 2,000 J / cm2, such as less than 1,750 J / cm2.

[0236] Aspect 92. The method of any of aspects 29 to 91, wherein a total energy density required to cure the composition was reduced by at least 5% compared to a total energy density required to cure a composition that did not comprise the photothermally active material, such as reduced by at least 10%.

[0237] Aspect 93. The method of any of aspects 29 to 92, wherein a total energy density required to cure the composition was reduced by at least 15% compared to a total energy density required to cure a composition that did not comprise the photothermally active material, such as reduced by at least 20%.

[0238] Aspect 94. The method of aspects 29 to 93, wherein a total energy density required to cure the composition was reduced by at least 30% compared to a total energy density required to cure a composition that did not comprise the photothermally active material, such as reduced by at least 40%.

[0239] Aspect 95. The method of any of aspects 29 to 94, wherein a total energy density required to cure the composition was reduced by at least 50% compared to a total energy density required to cure a composition that did not comprise the photothermally active material, such as reduced by at least 55%.

[0240] Aspect 96. The method of any of aspects 26 to 95, wherein a temperature of the substrate following exposure to the EMR is below a heat deflection temperature of the substrate.

[0241] Aspect 97. A substrate comprising a coating formed from the composition cured by the method of any of the preceding aspects.

[0242] Aspect 98. The substrate of aspect 97, wherein the coating was cured on demand.

[0243] Aspect 99. The substrate of aspect 97 or aspect 98, wherein the cured coating has a Shore A hardness of at least 50 measured according to ASTM D2240-15 following the exposure to EMR and cooling the coating to ambient temperature, such as a Shore A hardness of at least 55.

[0244] Aspect 100. The substrate of any of aspects 97 to 99, wherein the cured coating has a Shore A hardness of at least 60 measured according to ASTM D224-15 following the exposure to EMR and cooling the coating to ambient temperature, such as a Shore A hardness of at least 65.

[0245] Aspect 101. The substrate of any of aspects 97 to 100, wherein the cured coating has a Shore A hardness of at least 70 measured according to ASTM D2240-15 following the exposure to EMR and cooling the coating to ambient temperature.

[0246] Aspect 102. The substrate of any of aspects 97 to 101, wherein the cured coating has a final Shore A hardness of at least 55 measured according to ASTM D2240-15 at 24 hours after the exposure to EMR, such as a final Shore A hardness of at least 60.

[0247] Aspect 103. The substrate of any of aspects 97 to 102, wherein the cured coating has a final Shore A hardness of at least 65 measured according to ASTM D2240-15 at 24 hours after the exposure to EMR, such as a final Shore A hardness of at least 70.

[0248] Aspect 104. The substrate of any of aspects 97 to 103, wherein the cured coating has a final Shore A hardness of at least 75 measured according to ASTM D2240-15 at 24 hours after the exposure to EMR.

[0249] Aspect 105. The substrate of any of aspects 97 to 104, wherein the cured coating is cohesive.

[0250] Aspect 106. The substrate of any of aspects 97 to 105, wherein the coating is an undercoat, a sealant, an adhesive such as a structural adhesive, an anti-flutter coating, a sound damper, a pottant, a pre-preg, a liquid shim, and / or a gap filler.

[0251] Illustrating the disclosure are the following examples, which, however, are not to be considered as limiting the disclosure to their details.EXAMPLESTable 1: Compositions 1 to 6’A low density automotive polyvinyl chloride-based sealant commercially available from PPG Industries, Inc.2Monarch 120 carbon black, commercially available from Cabot Corporation (Boston, MA)3Copper phthalocyanine, commercially available from Penn Color, Inc. (Doylestown, PA)

[0252] Preparation of Compositions 1 to 6. At the application stage, 95g of the commercial material, PP4400S, was weighed into a plastic cup and, where applicable, the photothermally active material (“PT, carbon black or Astrad IS PCN Blue) was added. The complete formulation was then mixed vigorously by hand with a wooden tongue depressor for 2 minutes. Each sample was drawn down at a 3 mm thickness, using 3 mm shims, for all testing. All samples were drawn down on MEK-cleaned 7075-T6 Al substrates. Each aluminum substrate was subjected to a chemical deoxidizing pretreatment comprised of four steps: (i) rinsed in acetone for 1 min, (ii) rinsed in deionized water for 1 min, (iii) soaked in a CDX395 deoxidizing bath (commercially available from PPG Industries, Inc., prepared according to manufacturer’s instructions) equilibrated to 100°F for 1 min, and (iv) rinsed in deionized water for 1 min. Cure of the samples was monitored for 24 hours, at which point final Shore A hardness was recorded for all samples.

[0253] Adhesion test. Adhesion was tested for all cured samples by using a metal blade to separate a small portion of the drawn down sealant from the surface of the panel, then pulling the coating at a 90° angle relative to the surface of the panel. If the sealant cleanly delaminated from the panel (i.e. adhesive failure), the result was considered a “fail.” If the sealant left a thin film of material on the panel (i.e. thin-film cohesive failure) or failed cohesively, the result was considered a “pass.” Data are reported in Table 4.

[0254] Laser exposed samples. The defocused laser unit used for all studies was a Compact Heating and Drying SYS-CD system supplied by IPG Photonics® Corporation (Marlborough, MA) outfitted with a Class I laser, laser wavelength of 960 nm to 985 nm (model number DLS-4500-U-ECO) projected onto a 20cm x 20cm area using an enclosure (model number SYSMACDHE000004U). Compositions were drawn down on MEK-cleaned and chemically deoxidized 7075-T6 Aluminum substrates as described above. Compositions were exposed to the laser with a 30 second ramp from ambient to 140°C and then held at 140°C for 30 minutes. Shore A hardness was measured according to ASTM D2240-15 after the coating cooled to ambient temperature. Data are reported in Table 2.

[0255] Oven exposed samples. Compositions drawn down on MEK-cleaned and chemically deoxidized 7075-T6 Al substrates as described above. Compositions were placed in an oven at 140°C for 30 minutes. Shore A hardness was measured after the coating cooled to ambient temperature as described above. Data are reported in Table 3.

[0256] Total Energy Density calculation. Total Energy Density was calculated according to Equation 1 described above. Data are reported in Table 5.Table 2: Shore A Hardness Cure Profile Post-Laser ExposureTable 3: Shore A Hardness Cure Profile Post-Oven ExposureTable 4: Final Shore A Hardness and Adhesion Testing* Measured at 24 hr; repeated from Table 2 above** Measured at 24 hr; repeated from Table 3 aboveTable 5: Total Energy Density

[0257] For each of the samples, no significant difference was observed in the extent of cure between the laser-cured samples and the oven -cured samples. Each had a measurable Shore A hardness after its respective heating cycle, and final Shore A hardness was observed by 24 h. All samples passed the panel adhesion test described above. It was notable that Composition 1, the control, required more energy over time in its laser cure cycle versus the samples containing PT active material. Examples 2 and 3, which contained photothermally active carbon black, afforded the largest decrease in total energy density required to achieve the cure temperature of 140°C during the time period tested. Examples 4 to 6, which contained photothermally active Astrad IS PCN blue, also decreased the total energy density required to achieve the cure temperature of 140°C during the time period tested, although the total energy density required to achieve the cure temperature of 140°C was higher in compositions containing Astrad IS PCN blue compared to compositions containing carbon black, indicating that carbon black is a more effective photothermally active material in the thermoplastic compositions tested.

[0258] 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 thermoplastic polymer and a plasticizer.

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 exposing is for at least 30 minutes.

7. The method of any of the preceding claims, wherein a total energy density of up to 3,688 J / cm2is required to cure the composition.

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

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

10. The method of claim 8 or claim 9, 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 weight of the composition.

11. The method of any of claims 8 to 10, wherein a total energy density of up to 3,338 J / cm2is required to cure the composition.

12. The method of any of claims 8 to 11, wherein a total energy density required to maintain the composition at a preset temperature was reduced by at least 5% compared to a total energy density required to maintain a composition that did not comprise the photothermally active material.

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

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

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

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

17. The substrate of claim 16, wherein the coating has a Shore A hardness of at least 20 measured at least 60 minutes following the exposure to the EMR; wherein the Shore A hardness is measured according to ASTM D2240-15 following exposure to EMR and after the coating is cooled to ambient temperature.

18. The substrate of claim 16 or claim 17, wherein the coating has a Shore A hardness of at least 55 at least 24 hours following the exposure to EMR; wherein the Shore A hardness is measured according to ASTM D2240-15.

19. The substrate of any of claims 16 to 18, wherein the coating is cohesive.

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