Methods of curing hydrolysable compositions

Abstract

Disclosed are methods of curing a composition. The method includes exposing the composition to electromagnetic radiation generated by a laser to cure the composition. The composition may include a hydrolysable component and optionally a photothermally active material. Also disclosed are substrates comprising a coating formed from a composition cured by the disclosed methods.

Description

METHODS OF CURING HYDROLYSABLE COMPOSITIONSCROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to U.S. Provisional Application No. 63 / 714,485, filed on October 31, 2024, and entitled “Moisture Cured 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 hydrolysable component using electromagnetic radiation are disclosed.BACKGROUND

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

[0004] Disclosed are methods of curing a composition, comprising exposing the composition to electromagnetic radiation generated by a defocused laser to cure the composition; wherein the composition comprises a hydrolysable component.

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

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

[0007] As described in more detart below, the composition may comprise a hydrolysable component and optionally 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 isvisible 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 beelectrically connected such that the decline or farture 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 pigtart-coupled, to more than one fiber or may be configured as a bundle of fibers. As used herein, “pigtart-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 tartoring 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 trarter, 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;Equation 1, where Etot= total energy density in J / cm2; to = time zero or start of heating cycle; tmax = time to end of heating cycle, wherein the time from to to tmaxincludes ramp time to a temperature setpoint and hold time at the temperature setpoint (in seconds); %P - the percentage of laser power used in the recorded time interval (as recorded using LASCON Process Manager software by Dr. Mergenthaler GmbH & Co. KG, as part of the controller of the laser system; Lp = laser power, 4500 W; At - 0.02 seconds between recorded data points,; and A = the projection area of the laser output, 400 cm2. As used herein, “temperature setpoint” refers to a preset temperature to which the coating is ramped and at which the coating is maintained overthe heating cycle. Temperature setpoint may be measured using an infrared thermometer or similar device to measure the temperature of the coating. Temperatures from the infrared thermometer may be read by the controller described above to adjust the EMR generated by the laser system over the heating cycle to ramp or maintain the coating temperature at the temperature setpoint.

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

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

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

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

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

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

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

[0042] The photothermally active material that may be used in the compositions disclosed herein also include carbon black; graphite; graphene; and / or graphenic carbon particles. Graphene may be a thermal graphene such as turbostatic thermal graphene. Graphene may be in the form of commercially avartable 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 stacking associated with conventional exfoliated graphene but rather exhibit disordered or non- AB AB AB stacking. Alternatively, the graphenic carbon particles may be in the form of nanotubes. The particles typically do not have a spheroidal or equiaxed morphology.

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

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

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

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

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

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

[0050] The photothermally active material may comprise carbon black 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, the photothermally active material may comprise a single photothermal material or may comprise two or more different types of photothermal 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 least 0.01 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 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, such as no more than 10 percent by weight. The composition maycomprise 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 15 percent by weight, such as 1 percent by weight to 10 percent by weight.Hydrolysable Components

[0056] The composition comprises a hydrolysable component. The hydrolysable component may be a silane-containing component comprising a hydrolysable group, a silyl-containing component comprising a hydrolysable group, and / or an imine-containing component comprising a hydrolysable group, as described in more detart below.

[0057] The composition may comprise the hydrolysable component in an amount of at least 1 percent by weight based on total weight of the composition, such as at least 5 percent by weight, such as at least 10 percent by weight, such as at least 15 percent by weight, such as at least 30 percent by weight. The composition may comprise the hydrolysable component in an amount of no more than 99.9999 percent by weight based on total weight of the composition, such as no more than 98.99 percent by weight, such as no more than 80 percent by weight, such as no more than 70 percent by weight, such as no more than 60 percent by weight. The composition may comprise the hydrolysable component in an amount of 1 percent by weight to 99.9999 percent by weight based on total weight of the composition, such as 5 percent by weight to 98.99 percent by weight, such as 10 percent by weight to 80 percent by weight, such as 15 percent by weight to 70 percent by weight, such as 30 percent by weight to 60 percent by weight.

[0058] The composition optionally may comprise a curing agent having a functional group capable of reacting with a functional group of the hydrolysable component after hydrolysis, such as a curing agent comprising an electrophilic functional group. As described in more detart below, suitable curing agents include an acetoacetate, an acrylate, an epoxide, a Michael acceptor, and / or an isocyanate.

[0059] The composition may comprise the curing agent in an amount of at least 1 percent by weight based on total weight of the composition, such as at least 5 percent by weight, such as at least 10 percent by weight, such as at least 20 percent by weight. The composition may comprise the curing agent 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 70 percent by weight, such as no more than 60 percent by weight, such as no more than 50 percentby weight. The composition may comprise the curing agent in an amount of 1 percent by weight to 90 percent by weight based on total weight of the composition, such as 1 percent by weight to 80 percent by weight, such as 5 percent by weight to 70 percent by weight, such as 10 percent by weight to 60 percent by weight, such as 20 percent by weight to 50 percent by weight.

[0060] As described in more detart below, the hydrolysable group of the present disclosure may have the general formula (I):Zn_ l _Y X(m-n) (I)wherein when Y=Si, then m=3, n=0, and X=H, an alkoxy, an acyloxy, or a halogen, and wherein Z= an organo-carbon chain, an alkyl, a branched alkyl, or a substituted alkyl; and wherein when Y=S, then m=1, n=1, Z==H, an organo-carbon chain, an alkyl, a branched alkyl, or a substituted alkyl, and X=a silyl group containing an alkyl group, a branched alkyl group, a substituted alkyl group, or a phenyl group; and wherein when Y=C (i.e., more than 1 hydrolysable group), then m=l, n=0 and X=nitrogen. As used herein, “silyl group” refers to the following formula (II):wherein R3, R4, and R5are each independently selected from a Ci-6 n-alkyl group, a Ci-6 branched alkyl group, a substituted Ci-6 n-alkyl group, and a phenyl group and may be the same or different.

[0061] Upon exposure to water or moisture, the hydrolysable group may react with water to form a hydrolyzed product, such as an -Si-OH and / or an -SH and / or an -NH or -NH2. Selfcondensing hydrolysable components are those that are capable of condensing to form a condensed product without a curing agent (although as described below, curing agents optionally may be used in such coating compositions).

[0062] Optionally, the hydrolysable component may be substantially free, essentially free, or completely free of a silicone-containing species having the formula (III):wherein R16, R17 and R18 are independently selected from the group consisting of H, alkyl, aryl, cycloalkyl, alkoxy, aryloxy, hydroxyalkyl, alkoxyalkyl and hydroxy-alkoxyalkyl groups containing up to six carbon atoms, and where R19 is selected from the group consisting of H and alkyl and aryl groups containing up to six carbon atoms, and “n” is greater than 1.Silane-Containing Moisture Curable Resin Systems

[0063] The hydrolysable component of the present disclosure may comprise a silane-containing polymer. The silane-containing polymer may be any silane-containing polymer containing hydrolysable groups that are capable of self-condensing.

[0064] The silane-containing polymer may be a single silane-containing polymer or a combination of silane-containing polymers. The silane-containing polymer includes hydrolysable groups attached to the Si atom. Non-limiting examples of suitable hydrolysable groups for attachment to the Si atom of the silane group include alkoxy groups, acyloxy groups, halogen groups, amino groups, or combinations thereof.

[0065] Suitable examples of silane-containing polymers useful in the present disclosure include polyepoxides, polythioethers, polythiols, polyesters, polyethers, polyolefins, polyureas, polyurethanes, polyisocyanates, poly(meth)acrylates, or combinations thereof. As used herein, “polythioether” refers to a polymer having a backbone including S atoms, but which does not include S — S linkages, i.e., the polymer backbone has — C — S — C — linkages.

[0066] Suitable silane-containing polymers include the polythioethers disclosed in U. S. Patent No. 8,143,370, col. 2, 11. 15-col.3, 11. 4, incorporated herein by reference. For example, silane-terminated polythioethers can be prepared by reacting a mercapto-terminated polythioether with a compound having a silane group. Any suitable mercapto-teiminated polythioether may be used. For example, the mercapto-terminated polythioether used in the reaction to make the silane-terminated polythioether may be a mercapto-terminated polythioether represented by formula IV, below.H— [S— Ri— S— (CH2)P— O— (R2— O— )m— (CH2)q]u— S— Ri— SH (IV)In formula(IV), Ri may be selected from C2to Cion-alkylene groups, C2to Cr> branched alkylene groups, Ceto Cx cycloalkylene groups, Ceto Cioalkylcyloalkylene groups, heterocyclic groups, — [(CH2)P— X]q— (CH2)I — groups, and — [(CH2)P— X]q— (CH2)I — groups in which at least one — CH2— unit is substituted with a methyl group. R2may be selected from C2to C10 n-alkylenegroups, C2 to Q, branched alkylene groups, Ceto Cx cycloalkylene groups, CetoC14 alkylcyloalkylcnc groups, heterocyclic groups, and — [(CH2)P— X]q— (CH2)I — groups. X may be selected from O atoms, S atoms, and — NR3 — groups. R3 may be selected from H and methyl groups. Also, in formula (IV), m is an integer ranging from 1 to 50, n is an integer ranging from 1 to 60, p is an integer ranging from 2 to 6, q is an integer ranging from 1 to 5, and r is an integer ranging from 2 to 10. Non-limiting examples of suitable compounds having silane groups for reaction with the poly thioether include silane-terminated vinyl compounds, silane-terminated isocyanate compounds, and silane-terminated epoxy compounds. The silane group includes hydrolysable groups attached to the Si atom. In particular, the silane group may be represented by — Si(YaAb), in which Y is a functional group, for example an alkoxy, a halogen, or an acetoxy group, that is both hydrolysable and condensable, A is a Ci to C4 hydrocarbon, a ranges from 1 to 3, b ranges from 0 to 2, and a+b=3.

[0067] Additional non-limiting examples of suitable mercapto-terminated polythioether compounds include those disclosed in U. S. Patent No. 6,509,418, the entire content of which is incorporated herein by reference. The mercapto-terminated polymers may be prepared by reacting reactants comprising one or more polyvinyl ether monomers and one or more polythiol materials. Useful polyvinyl ether monomers include divinyl ethers having the formula (V): CH2=CH— O— (R2— O)m— CH=CH2(V)where R2is C2-6 n-alkylene, C2-6 branched alkylene, Ce-s cycloalkylene or Ce-io alkylcycloalkylene group or — [(CH2)P— O]q— (CH2)I — and m is a rational number ranging from 0 to 10, p is an independently selected integer ranging from 2 to 6, q is an independently selected integer ranging from 1 to 5, and r is an independently selected integer ranging from 2 to 10. Suitable poly thiol materials for preparing the mercapto-terminated polymer include compounds, monomers, or polymers having at least two thiol groups. Useful poly thiols include dithiols having the formula (VI):HS— R1— SH (VI)where R1can be a C2-6 n-alkylene group; C3-6 branched alkylene group, having one or more pendant groups which can be, for example, hydroxyl groups, alkyl groups such as methyl or ethyl groups; alkoxy groups, Ce-s cycloalkylcnc; Ce-io alkylcycloalkylcnc group; — [(CH2)P— X]q— (CH2)I —; or — [(CH2)P— X]q— (CH2)I — in which at least one — CH2 — unit is substituted with a methyl group and in which p is an independently selected integer ranging from 2 to 6, q isan independently selected integer ranging from 1 to 5 and r is an independently selected integer ranging from 2 to 10. Other useful dithiols include one or more hctcroatom substituents in the carbon backbone, that is, dithiols in which X includes a heteroatom such as O, S, or another bivalent heteroatom radical; a secondary or tertiary amine group; or a substituted trivalent heteroatom. Useful polythiols include but are not limited to dithiols such as 1,2-ethanedithiol, 1.2-propanedithiol, 1,3-propanedithiol, 1,3 -butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1.3-pentanedithiol, 1,5 -pentanedithiol, 1,6-hexanedithiol, l,3-dimercapto-3-methylbutane, dipentenedimercaptan, ethylcyclohexyldithiol (ECHDT), dimercaptodiethylsulfide, methylsubstituted dimercaptodiethylsulfide, dimethyl-substituted dimercaptodiethylsulfide, dimercaptodioxaoctane, l,5-dimercapto-3-oxapentane and mixtures thereof. The polythiol material can have one or more pendant groups selected from lower alkyl groups (such as Ci-Ce ), lower alkoxy groups (such as Ci-Ce), and hydroxyl groups. Suitable alkyl pendant groups include Ci-Ce linear alkyl, Ca-Ce branched alkyl, cyclopentyl, and cyclohexyl.

[0068] In other examples, the silane-containing polymer may comprise a polyester.

[0069] The term “polyester” comprises any polymer containing ester functional groups that are generally prepared from the reaction of polyacids with polyols, carboxylic acid derivatives (i.e., acid chlorides, anhydrides) with polyols, the self-condensation of polylactones, or combinations thereof. Silane-containing polyester can be prepared by reacting a polyester with a compound containing silane. Suitable examples are polyester polyols which are prepared from dihydroxyls such as 1,2-ethanediol, diethylene glycol, 1,2-propanediol, dipropylene glycol, 1.4-butanediol, or mixtures of said alcohols, and organic dicarboxylic acids or anhydrides or esters thereof, such as succinic acid, glutaric acid, adipic acid, trimethyladipic acid, phthalic anhydride, terephthalic acid, or mixtures thereof.

[0070] In other examples, the silane-containing polymer may comprise a polyether.

[0071] The terms “polyether” is intended to include not only polyethers that are formed from ring opening polymerization of cyclic compounds, such as ethylene oxide, 1,2-propylene oxide, 2,3-butylene oxide, and mixtures of said compounds, but also polyethers that are formed from polycondensation of compounds containing two or more active hydrogen atoms, such as 1,2-ethanediol, neopentyl glycol, diethylene glycol, and mixtures of said compounds. Silane-containing polyether can be prepared by reacting a polyether with a compound containing silane.Suitable examples are polyether-containing hydroxyl groups, such as polyoxyethylene polyols and polyoxypropylene polyols.

[0072] In other examples, the silane-containing polymer may comprise a polyurethane.

[0073] The term “polyurethane” is intended to include not only polyurethanes that are formed from the reaction of polyisocyanates and polyols but also poly(ureaurethane)(s) that are prepared from the reaction of polyisocyanates with polyols and water and / or amines. Silane-containing polyurethanes can be prepared by reacting polyisocyanates with a compound containing silane.

[0074] In other examples, the silane-containing polymer may comprise a polyurea.

[0075] The term “polyurea” is intended to include polyureas that are formed from the reaction of polyisocyanates and polyamines. Silane-containing polyurethanes can be prepared by reacting polyisocyanates with a compound containing silane.

[0076] In other examples, the silane-containing polymer may comprise a polyisocyanate.

[0077] Non-limiting examples of suitable polyisocyanates in the present disclosure include polyisocyanates and polyisothiocyanates having backbone linkage such as urethane linkage (-NH-C(O)-O-), thiourethane linkages (-NH-C(O)-S-), thiocarbamate linkages (-NH-C(S)-O-), dithiourethane linkages (-NH-C(S)-S-), polyamide linkages, and combinations thereof. Suitable polyisocyanates are aliphatic isocyanates including ethylene diisocyanate, trimethylene diisocyanate, 1,6-hexamethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, branched isocyanates such as trimethylhexane diisocyanate, trimethylhexamethylene diisocyanate, and mixtures thereof. More examples of polyisocyanates are described in U. S. Publ. No. 2016 / 0333133 Al at pars.

[0073] to

[0088] , incorporated herein by reference.

[0078] In other examples, the silane-containing polymer may comprise a polyolefin.

[0079] The term “polyolefin” is intended to include polyolefins that are prepared by polymerization of olefin monomers, such as C2-C20 a-olefins including ethylene, propylene, 1-X-butene, and mixtures of said monomers. Silane-containing polyolefins can be prepared by reacting a polyolefin with a compound containing silane such as silazane. Suitable examples of polyolefins include, but are not limited to, INFUSE™ olefin block copolymers (commercially avartable from the Dow Chemical Company), SEPTON™ V - SERIES hydrogenated styrenic thermoplastic elastomers (commercially avartable from Kuraray Co., LTD.), VISTAMAXX™polyolefins (e.g., VTSTAMAXX 6102) (commercially avartable from Exxon Mobil Chemical Company), TAFMER™ propylene based elastomers (e.g., TAFMER DF710) (commercially avartable from Mitsui Chemicals, Inc.), and ENGAGE™ polyolefins (e.g., ENGAGE 8150) (commercially avartable from the Dow Chemical Company).

[0080] In other examples, the silane-containing polymer may comprise a poly(meth)acrylate.

[0081] Silane-containing poly(meth)acrylates may be prepared by a copolymerization of (meth)acryloyloxyalkyalkoxysilanes with other (meth)acryloyl monomers and / or further unsaturated monomers, such as styrene, but also prepared by reacting poly(meth)acrylate with a silane compound.

[0082] The silane-containing polymer may also comprise at least one silane-terminated polymer. The silane-terminated polymer may be capable of crosslinking in the presence of moisture. The polymer may be an alkoxysilane-terminated polyether, an alkoxysilane-terminated polyurethane, or combinations thereof. The alkoxysilane can be methoxy or ethoxy silane, with one, two, or three alkoxy groups per silane. Commercial examples of alkoxysilane-terminated polymers include the Kaneka MS polymers such as SAX 350, SAX 400, and SAX 750 or the Wacker STP-E series such as STP-E30.

[0083] The silane-containing polymer may be present in the composition in an amount of at least 10 percent by weight based on total weight of the composition, such as at least 15 percent by weight, such as no more than 99.9999 percent by weight, such as no more than 80 percent by weight, such as 10 percent by weight to 99.9999 percent by weight, such as 15 percent by weight to 80 percent by weight.Silyl-Containing Moisture Curable Resin Systems

[0084] The silyl-containing polymer may be a single silyl -containing polymer or a combination of silyl-containing polymers. The silyl-containing polymer includes hydrolysable groups attached to an S atom. The silyl-containing functional group within the polymer may comprise an alkyl group, a phenyl group, or combinations thereof. For example, non-limiting examples of suitable substituted hydrolysable groups attached to the S atom contain a Si atom substituted with groups including Ci-6 n-alkyl groups, Ci-6 branched alkyl groups, substituted Ci-6 n-alkyl groups, phenyl groups, or combinations thereof.

[0085] Suitable examples of silyl-containing polymers useful in the present disclosure include sulfur-containing polymers such as substituted poly thioethers, substituted polysulfides, substituted thiol esters, substituted thiol polyacrylates, or combinations thereof. A polysilyl-terminated sulfur-containing polymer can be any polymer having at least one sulfur atom in the repeating unit, including, but not limited to, polythiols, thioethers, poly thioethers, sulfur-containing polyformals, and poly sulfides.

[0086] Useful mercapto-terminated polythioethers include those described in WO 2011 / 005614A1, pars.

[0009] -

[0016] , incorporated herein by reference, and can be produced by reacting a divinyl ether or mixtures of divinyl ethers with an excess of dithiol or mixtures of dithiols. In some examples, the mercapto-terminated polythioether used in the reaction to make the silyl-terminated polythioether may be a mercapto-terminated polythioether represented by formula (IX), below. Mercapto-terminated polythioethers useful in the formation of the present disclosure have a terminal mercapto functionality of at least 2.H-[S-Ri-S-(CH2)p-O-(R2-O-)m-(CH2)q]n-S-Rl -SH (IX)

[0087] In formula IX, Ri may be selected from C2to Cio n-alkylene groups, C2to Ce branched alkylene groups, Ceto Cs cycloalkylene groups, Ce to Cio alkylcycloalkylene groups, heterocyclic groups, -[(CH2)p-X]q-(CH2)r- groups, and -[(CH2)p-X]q-(CH2)r- groups in which at least one -CH2- unit is substituted with a methyl group. R2may be selected from Ci to Cio n-alkylene groups, C2to Ce branched alkylene groups, Ce to Cx cycloalkylene groups, Ce to Ci4 alkylcycloalkylene groups, heterocyclic groups, and -[(CH2)p-X]q-(CH2)r- groups. X may be selected from O, S, and -NR3- groups. R3may be selected from H and alkyl groups. Also, in formula IX, m is an integer ranging from 1 to 50, n is an integer ranging from 1 to 60, p is an integer ranging from 2 to 6, q is an integer ranging from 1 to 5, and r is an integer ranging from 2 to 10. In one embodiment, for example, Ri is a C2to Ce alkyl group and R2is a C2to Ce alkyl group.

[0088] In an example, the mercapto-terminated poly thioether component may be represented by a mercapto-terminated polythioether of formula IX, where Ri is -[(CH2)P-X]q-(CH2)r-, p is 2, X is O, q is 2, r is 2, R2is an ethylene group, m is 2, and n is 9. In an alternate embodiment of the mercapto-terminated polythioether, m is 1, R2is n- butylene, and Ri is not ethylene or n-propylene. In another example, m is 1, p is 2, q is 2, r is 2, R2is ethylene, and X is not an O atom.

[0089] In examples, the silyl-containing polymer may comprise at least two groups, per molecule, having the formula (II) set forth above.

[0090] In examples, the silyl-containing polymer may have an average functionality of 2 to 6.

[0091] The silyl-containing polymer may be present in the composition in an amount of at least 1.5 percent by weight based on total weight of the composition, such as at least 8 percent by weight, such as at least 15 percent by weight, such as at least 30 percent by weight, and may be present in the composition in an amount of no more than 98.99 percent by weight based on total weight of the composition, such as no more than 80 percent by weight, such as no more than 70 percent by weight, such as no more than 60 percent by weight. The silyl-containing polymer may be present in the composition in an amount of 1.5 percent by weight to 98.99 percent by weight based on total weight of the composition, such as 8 percent by weight to 80 percent by weight, such as 15 percent by weight to 70 percent by weight, such as 30 percent by weight to 60 percent by weight.Imine -Containing Moisture-Curable Resin Systems

[0092] Suitable examples of imines useful in the present disclosure include ketimines, aldimines, or combinations thereof.

[0093] Ketimines are typically prepared by the reaction of ketones with amines.Examples of ketones may include acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, diethyl ketone, benzyl methylketone, diisopropyl ketone, cyclopentanone, and cyclohexanone. Examples of amines may include ethylene diamine, ethylene triamine, propylene diamine, tetramethylene diamine, 1,6-hexamethylene diamine, bis(6-aminohexyl) ether, tricyclodecane diamine, N, N'-dimethyldiethyltriamine, cyclohexyl- 1, 2, 4-triamine, cyclohexyl- 1,2,4, 5-tetraamine, 3,4,5-triaminopyran, 3,4-diamino furan, and cycloaliphatic diamines such as those having the following formula:Formula (XXII).

[0094] Aldimines are typically prepared by the reaction of aldehydes with amines.

[0095] Examples of aldehydes may include acetaldehyde, formaldehyde, propionaldehyde, isobutyraldehyde, n-butyraldehyde, heptaldehyde, and cyclohexyl aldehydes. Examples of amines may include ethylene diamine, ethylene triamine, propylene diamine, tetramethylene diamine, 1,6-hexamethylene diamine, bis(6-aminohexyl) ether, tricyclodecane diamine, N, N'-dimethyldiethyltriamine, cyclohexyl- 1,2, 4-triamine, cyclohexyl- 1,2, 4,5-tetraamine, 3, 4, 5 -triaminopyran, 3,4-diamino furan, and cycloaliphatic diamines such as those having the following structures:Formula (XXVI);Formula (XXVII); Formula (XXVIII);Formula (XXIX);Formula (XXXIV); and / orFormula (XXXV).

[0096] The composition may comprise the imine in an amount of at least 1.5% by weight based on total weight of the composition, such as at least 8% by weight, such as at least 15% by weight, such as at least 30% by weight, and may be present in the composition in an amount of no more than 98.99% by weight based on total weight of the composition, such as no more than 80% by weight, such as no more than 70% by weight, such as no more than 60% by weight. The imine may be present in the composition in an amount of 1.5% by weight to 89.5% by weight based on total weight of the composition, such as 8% by weight to 80% by weight, such as 15% by weight to 70% by weight, such as 30% by weight to 60% by weight.Curing Agents

[0097] Although the silane-containing polymers are capable of self-condensing, the composition optionally may further comprise a curing agent. Suitable curing agents for use with the silane-containing polymers include silanols, polyols, and polythiols.

[0098] As discussed above, such a curing agent may comprise a silanol. Suitable silanols can be represented by the formula (Rn’)Si(OH)m(where m>0, n+m = 4, and each R’ independently is the same or different kind of substituted or non-substituted alkyl group, aryl group, cycloalkyl group, or heterocyclic group). Non-limiting examples are tris(tert-butoxy)silanol, tris(ter-pentoxy)silanol, tris(trimethylsilyl)silanol, p-fluorohexahydro- siladifenidol hydrochloride, tri(o-tolyl)silanol, tris(1-naphthyl)silanol, tris(2,4,6-trimethylphenol)silanol, tris(2-methoxylphenyl)silanol, tris(4-(dimethylamino)phenyl)silanol, and mixtures thereof.

[0099] As discussed above, such a curing agent may comprise a polyol. Suitable polyols can be a cycloalkane diol, such as cyclopentanediol, 1,4-cyclohexanediol, cyclohexanedimethanols, such as 1,4-cyclohexanedimethanol, cyclododecanediol, 4,4'-isopropylidene-biscyclohexanol, hydroxypropoylcyohexanol, cyclohexandiethanol, 1,2-bis(hydroxymethyl)-cyclohexane, 1,2-bis(hydroxyethyl)-cyclohexane, 4,4'-isopropylidene-biscyclohexanol, bis(4-hydroxycyclohexanol)methane, and mixtures thereof. The polyols can be an aromatic diol, such as dihydroxybenzene, xylene glycol, hydroxybenzyl alcohol, and dihydroxy toluene; bisphenols, such as, 4,4’-isopropylidenediphenol, 4’4’oxybisphenol, hydroquinone, and mixtures thereof.

[0100] Other suitable examples include diols represented by the following formula (XXXVI):(XXXVI)wherein R represents a Ci to Cis divalent linear or branched aliphatic, cycloaliphatic, aromatic, heterocyclic, or oligomeric saturated alkylene radical or mixtures thereof; a C2 to Cis divalent organic radical containing at least one element selected from the group consisting of sulfur, oxygen and silicon in addition to carbon and hydrogen atoms; C5 to Cis divalent saturated cycloalkylene radical; or a C5 to Cis divalent saturated heterocycloalkylene radical; and R' and R" can be present or absent and, if present, each independently represents a Ci to Cis divalent linear or branched aliphatic, cycloaliphatic, aromatic, heterocyclic, polymeric, or oligomeric saturated alkylene radical or mixtures thereof.

[0101] Other non-limiting examples of suitable diols include branched chain alkane diols, such as propylene glycol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 2- methyl-butanediol. 2,2,4-trimethyl-l,3-pentanediol, 2-methyl-l,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, dibutyl 1,3-propanediol, polyalkylene glycols, such as polyethylene glycols, and mixtures thereof.

[0102] In some non-limiting examples, the diol can be an aromatic-containing diol, such as dihydroxybenzene, 1,4-benzenedimethanol, xylene glycol, hydroxybenzyl alcohol, and dihydroxy toluene; bisphenols, such as, 4,4'-isopropylidenediphenol, 4,4'-oxybisphenol, 4,4'- dihydroxybenzophenone, 4,4'-thiobisphenol, phenolphthalein, bis(4-hydroxyphenyl)methane, 4,4'-(l,2-ethenediyl)bisphenol, and 4,4'-sulfonylbisphenol; halogenated bisphenols, such as 4,4'- isopropylidenebis(2,6-dibromophenol), 4,4'-isopropylidenebis(2,6-dichlorophenol), and 4,4'- isopropylidenebis(2,3,5,6-tetrachlorophenol); alkoxylated bisphenols, which can have, for example, ethoxy, propoxy, a-butoxy and -butoxy groups; and biscyclohexanols, which can be prepared by hydrogenating the corresponding bisphenols, such as 4,4'-isopropylidene-biscyclohexanol, 4,4'-oxybiscyclohexanol, 4,4'-thiobiscyclohexanol andbis(4-hydroxycyclohexanol)methane, the alkoxylation product of 1 mole of 2,2-bis(4-hydroxyphenyl)propane (i.e., bisphenol-A) and 2 moles of propylene oxide, hydroxyalkyl terephthalates, such as meta or para bis(2-hydroxyethyl) terephthalate, bis(hydroxyethyl) hydroquinone, and mixtures thereof.

[0103] In some non-limiting examples, the diol can be a heterocyclic diol, for example a dihydroxy piperazine such as 1,4-bis(hydroxyethyl)piperazine, a diol of an amide or alkane amide (such as ethanediamide (oxamide)), for example N, N'-bis(2-hydroxyethyl)oxamide, a diol of a propionate, such as 2,2-dimethyl-3-hydroxypropyl-2,2-dimethyl-3-hydroxypropionate, a diol of a hydantoin, such as bishydroxy propyl hydantoin, a diol of a phthalate, such as meta or para bis(2-hydroxyethyl) terephthalate, a diol of a hydroquinone, such as a dihydroxyethylhydroquinone, and / or a diol of an isocyanurate, such as dihydroxyethyl isocyanurate.

[0104] Non-limiting examples of polyether polyols can include but are not limited to polyoxyalkylene polyols, and polyalkoxylated polyols. Polyoxyalkylene polyols can be prepared in accordance with known methods. In a non-limiting example, a polyoxy alkylene polyol can be prepared by condensing an alkylene oxide, or a mixture of alkylene oxides, using acid-or basecatalyzed addition with a polyhydric initiator or a mixture of polyhydric initiators, such as but not limited to ethylene glycol, propylene glycol, glycerol, and sorbitol. Non-limiting examples of alkylene oxides can include ethylene oxide, propylene oxide, butylene oxide, amylene oxide, aralkylene oxides, such as but not limited to styrene oxide, mixtures of ethylene oxide and propylene oxide. In a further non-limiting example, polyoxyalkylene polyols can be prepared with mixtures of alkylene oxide using random or stepwise oxyalkylation. Non-limiting examples of such polyoxyalkylene polyols include polyoxyethylene, such as but not limited to polyethylene glycol, polyoxypropylene, such as but not limited to polypropylene glycol.

[0105] In a non-limiting example, polyalkoxylated polyols can be represented by the following general formula (XXXVII):wherein m and n can each be a positive integer, the sum of m and n being from 5 to 70; R1 and R2 are each hydrogen, methyl or ethyl; and A is a divalent linking group such as a straight or branched chain alkylene which can contain from 1 to 8 carbon atoms, phenylene, and Ci to C9 alkyl-substituted phenylene. The chosen values of m and n can, in combination with the chosen divalent linking group, determine the molecular weight of the polyol.

[0106] Polyalkoxylated polyols can be prepared by methods that are known in the art. In a non-limiting example, a polyol such as 4,4'-isopropylidenediphenol can be reacted with an oxirane-containing material such as but not limited to ethylene oxide, propylene oxide and butylene oxide, to form what is commonly referred to as an ethoxylated, propoxylated or butoxylated polyol having hydroxy functionality. Non-limiting examples of polyols suitable for use in preparing polyalkoxylated polyols can include those polyols described in U. S. Patent No.6,187,444 Bl at column 10, lines 1-20, which disclosure is incorporated herein by reference.

[0107] As used herein, the term “polyether polyols” can include the generally known poly(oxytetramethylene) diols prepared by the polymerization of tetrahydrofuran in the presence of Lewis acid catalysts, such as but not limited to boron trifluoride, tin (IV) chloride and sulfonyl chloride. In a non-limiting example, the polyether polyol can include Terathane™ which is commercially avartable from DuPont. Also included are the polyethers prepared by the copolymerization of cyclic ethers, such as but not limited to ethylene oxide, propylene oxide, trimethylene oxide, and tetrahydrofuran with aliphatic diols, such as but not limited to ethylene glycol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol, 1,2-propylene glycol and 1,3-propylene glycol. Compatible mixtures of polyether polyols can also be used. As used herein, “compatible” means that the polyols are mutually soluble in each other so as to form a single phase.

[0108] A wide variety of polyester polyols known in the art can be used in the present disclosure. Suitable polyester polyols can include but are not limited to polyester glycols.Polyester glycols for use in the present disclosure can include the esterification products of one or more dicarboxylic acids having from four to ten carbon atoms, such as but not limited to adipic, succinic or sebacic acids, with one or more low molecular weight glycols having from two to ten carbon atoms, such as but not limited to ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol and 1,10-decanediol. Esterificationprocedures for producing polyester polyols are described, for example, in the article D. M.Young, F. Hostettler, et al., “Polyesters from Lactone,” Union Carbide F-40, p. 147.

[0109] In a non-limiting example, the polyol for use in the present disclosure can include polycaprolactone polyols. Suitable polycaprolactone polyols are varied and known in the art. In a non-limiting example, polycaprolactone polyols can be prepared by condensing caprolactone in the presence of difunctional active hydrogen compounds such as but not limited to water or low molecular weight (such as those having an Mw of 6,000 or less) glycols as recited herein. Nonlimiting examples of suitable polycaprolactone polyols can include commercially avartable materials designated as the CAPA series from Solvay Chemical which includes but is not limited to CAPA 2047A, and the TONE™ series from The Dow Chemical Company, such as but not limited to TONE 0201.

[0110] Polycarbonate polyols for use in the present disclosure are varied and known to one skilled in the art. Suitable polycarbonate polyols can include those commercially avartable (such as but not limited to Ravecarb™ 107 from Enichem S.p. A.). In a non-limiting example, the polycarbonate polyol can be produced by reacting an organic glycol such as a diol, described hereinafter, and a dialkyl carbonate, such as described in U. S. Patent No. 4,160,853. In a nonlimiting example, the polyol can include polyhexamethyl carbonate such as HO — (CH2)6 — [O — C(O) — O — (CH2)6]n — OH, wherein n is an integer from 4 to 24, or from 4 to 10, or from 5 to 7.

[0111] As discussed above, the curing agents for use with the self-condensing silane-containing polymers may comprise a thiol, such as a polythiol curing agent. As used herein, a “polythiol curing agent” refers to a chemical compound having at least two thiol functional groups (-SH).

[0112] The polythiol curing agent may comprise a compound comprising at least two thiol functional groups. The polythiol curing agent may comprise a dithiol, trithiol, tetrathiol, pentathiol, hexathiol or higher functional polythiol compound, i.e. comprising seven or more thiol groups per molecule. The polythiol curing agent may comprise a dithiol compound including 3,6-dioxa- 1,8-octanedithiol (DMDO), 3-oxa-l,5-pentanedithiol, 1,2-ethanedithiol, 1,3-propanedithiol, 1,2-propanedithiol, 1,4-butanedithiol, 1,3-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,3-pentanedithiol, 1,6-hexanedithiol, l,3-dithio-3-methylbutane, ethylcyclohexyldithiol (ECHDT), methylcyclohexyldithiol, methyl-substituted dimercaptodiethyl sulfide, dimethyl-substituted dimercaptodiethyl sulfide, 2,3-dimercapto-l-propanol, bis-(4-mercaptomethylphenyl) ether, 2,2'-thiodiethanethiol, and glycol dimercaptoacetate (commercially avartable as THIOCURE® GDMA from BRUNO BOCK Chemische Fabrik GmbH & Co. KG). The poly thiol curing agent may comprise a trithiol compound including trimethylpropane trimercaptoacetate (commercially avartable as THIOCURE® TMPMA from BRUNO BOCK Chemische Fabrik GmbH & Co. KG), trimethylopropane tris-3-mercaptopropionate (commercially avartable as THIOCURE® TMPMP from BRUNO BOCK Chemische Fabrik GmbH & Co. KG), ethoxylated trimethylpropane tris-3-mercaptopropionate polymer (commercially avartable as THIOCURE® ETTMP from BRUNO BOCK Chemische Fabrik GmbH & Co. KG), tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate (commercially avartable as THIOCURE® TEMPIC from BRUNO BOCK Chemische Fabrik GmbH & Co. KG). The poly thiol curing agent may comprise a tetrathiol compound including pentaerythritol tetramercaptoacetate (commercially avartable as THIOCURE® PETMA from BRUNO BOCK Chemische Fabrik GmbH & Co. KG), pentaerythritol tetra-3-mercaptopropionate (commercially avartable as THIOCURE® PETMP from BRUNO BOCK Chemische Fabrik GmbH & Co. KG), and polycaprolactone tetra(3-mercaptopropionate) (commercially avartable as THIOCURE® PCL4MP 1350 from BRUNO BOCK Chemische Fabrik GmbH & Co. KG). Higher functional polythiol curing agents may include dipentaerythritol hexa-3-mercaptopropionate (commercially avartable as THIOCURE® DiPETMP from BRUNO BOCK Chemische Fabrik GmbH & Co. KG). Combinations of poly thiol curing agents may also be used.

[0113] The thiol curing agent may comprise a mercaptan terminated poly sulfide.Commercially avartable mercaptan terminated polysulfides include those sold under the trade name THIOKOL® LP from Toray Fine Chemicals Co., Ltd., including, but not limited to, LP-3, LP-33, LP-23, LP-980, LP-2, LP-32, LP-12, LP-31, LP-55 and LP-56. The THIOKOL LP mercaptan terminated polysulfides have the general structure HS-(C2H4-O-CH2-O-C2H4-S-S)nC2H4-O-CH2-O-C2H4-SH, wherein n is an integer of 5 to 50. Other commercially avartable mercaptan terminated polysulfides include those sold under the trade name THIOPLAST® G™ from Nouryon, including, but not limited to, GIO, G112, G131, Gl, G12, G21, G22, G44 and G4. The THIOPLAST G mercaptan terminated polysulfides are blends of di- and tri-functional mercaptan-functional polysulfides with the di-functional unit having the structure HS-(R-S-S)n-R-SH, wherein n is an integer from 7 to 38, and the tri-functional unit having the structure HS-(R-S-S)a-CH2-CH((S-S-R)c-SH)-CH2-(S-S-R)b-SH, wherein R is -C2H4-O-CH2-O-C2H4-, a + b + c = n and n is an integer from 7 to 38.

[0114] The thiol curing agent may comprise a mercaptan terminated polyether.Commercially avartable mercaptan terminated polyether include POLYTHIOL QE-340M avartable from Toray Fine Chemicals Co., Ltd.

[0115] The thiol optionally used in the coating composition of the present disclosure may have a calculated molecular’ weight of at least 94 g / mol, such as at least 490 g / mol, and may have a calculated molecular weight of no more than 2,000 g / mol, such as no more than 780 g / mol. The thiol of the present disclosure may have a calculated molecular weight of 94 g / mol to 2,000 g / mol, such as 490 g / mol to 780 g / mol.

[0116] Optionally, the thiol curing agent may be substantially free of disulfide (S-S) bonds. Substantially free, when used with respect to the absence of S-S bonds in the thiol curing agent, means that there is no detectable signal for these bonds above the noise in a Raman Spectrum, such as for example at 500 cm-1.

[0117] The composition comprising the silane-containing polymer may comprise the curing agent in an amount of at least 20 percent by weight based on total weight of the composition such as at least 40 percent by weight. The composition comprising the silane-containing polymer may comprise the curing agent in an amount of no more than 90 percent by weight based on total weight of the composition, such as no more than 75 percent by weight. The composition comprising the silane-containing polymer may comprise the curing agent in an amount of 20 percent by weight to 90 percent by weight based on total weight of the composition, such as 40 percent by weight to 75 percent by weight.

[0118] The moisture-curable composition comprising the silyl-containing polymer may further comprise a curing agent that reacts with the hydrolyzed component, such as a curing agent comprising a molecule comprising an electrophilic functional group, such as an acetoacetate, an acrylate, an epoxide, a Michael acceptor, an isocyanate, or combinations thereof.

[0119] As used herein, the term “acrylate-functional” moiety is understood to mean both substituted and non-substituted acrylate-functional ingredients. Suitable acrylate-functional ingredients include those selected from the group including acrylate-functional diluents, acrylate-functional oligomers, acrylate-functional polymers, and mixtures thereof.

[0120] Suitable acrylate-functional ingredients include those having the general chemical formula:R22[OCOCHCH]bR23where R22can be selected from the group including acrylic, polyester, polyether, and urethane polymers or diluents, or any hydroxy-functional polymer that is capable of being functionalized with [OCOCHCH], where “b” can be from 1 to 10, and where R23can be a hydrogen or can be a carbon-containing group having up to 6 carbon atoms.

[0121] Suitable (alkyl)acrylates include acids and esters thereof. For example, suitable curing agents include acrylate-functional oligomers such as trimethylolpropane triacrylate, tripropyleneglycol triacrylate, dipropylene glycol diacrylate, cyclohexanedimethanol diacrylate, hexanediol diacrylate, pentaerythritol tetraacrylate, di-trimethylolpropane triacrylate, neopentylglycol propoxylate diacrylate, ethoxylated trimethalpropane triacrylate, urethane acrylate oligomer, propoxylated glyceryl triacrylate, and aliphatic tetrafunctional polyester acrylate oligomer. Other suitable acrylate-functional diluents and oligomers include trimethalolpropane triacrylate avartable, for example, by Cognis of Exton, PA, under product name Photomer 4006; neopentylglycol propoxylate diacrylate avartable, for example by Cognis under product names Photomer 4126 and 4127; ethoxylated trimethylolpropane; triacrylate avartable, for example, by Cognis under product name Photomer 4129; and propoxylated glyceryl triacrylate avartable, for example, by Cognis under product name Photomer 4094.

[0122] Suitable acrylate-functional polymers include those having an acrylic, polyester, poly ether or urethane chemical backbone, including: aliphatic urethane triacrylate avartable, for example, from Cognis under the product name Photomer 6008; aliphatic urethane acrylate avartable under the product name Photomer 6893; aliphatic urethane diacrylate avartable under the product name Photomer 6210; urethane acrylate avartable, for example, from Sartomer of Exton Pa., under the product name CN968; epoxy acrylate from Sartomer under the product name CN104; epoxy novolac acrylate from Sartomer under the product name CN112; and polyester acrylate from Sartomer under the product name CN292 and from Cognis under the product name Photomer 5432.

[0123] Suitable epoxides that may be used in the compositions disclosed herein may comprise monoepoxides, diepoxides, and / or poly epoxides.

[0124] Suitable monoepoxides that may be used include monoglycidyl ethers of alcohols and phenols, such as phenyl glycidyl ether, n-butyl glycidyl ether, cresyl glycidyl ether, isopropyl glycidyl ether, glycidyl versatate, for example, CARDURA E avartable from Shell Chemical Co., and glycidyl esters of monocarboxylic acids such as glycidyl neodecanoate, Epodil 741 avartable from Evonik, Epodil 746 avartable from Evonik, ERISYS ® GE-7 avartable from CVC Thermoset Specialties, and mixtures of any of the foregoing.

[0125] Suitable polyepoxides include polyglycidyl ethers of Bisphenol A, such as Epon® 828 and 1001 epoxy resins, and Bisphenol F diepoxides, such as Epon® 862, which are commercially avartable from Hexion Specialty Chemicals, Inc. Other suitable polyepoxides include polyglycidyl ethers of polyhydric alcohols, polyglycidyl esters of polycarboxylic acids, polyepoxides that are derived from the epoxidation of an olefinically unsaturated alicyclic compound, polyepoxides that are derived from the epoxidation of an olefinically unsaturated nonaromatic cyclic compound, polyepoxides containing oxyalkylene groups in the epoxy molecule, and epoxy novolac resins. Still other suitable epoxy-containing compounds include epoxidized Bisphenol A novolacs, epoxidized phenolic novolacs, epoxidized cresylic novolac, and triglycidyl p-aminophenol bismaleimide. The epoxy-containing compound may also comprise an epoxy-dimer acid adduct. The epoxy-dimer acid adduct may be formed as the reaction product of reactants comprising a diepoxide compound (such as a polyglycidyl ether of Bisphenol A) and a dimer acid (such as a C36 dimer acid). The epoxy-containing compound may also comprise a carboxyl-terminated butadiene-acrylonitrile copolymer modified epoxy-containing compound. The epoxide also may comprise epoxidized castor oil. The epoxide also may comprise an epoxy-containing acrylic, such as glycidyl methacrylate. The epoxide also may comprise an epoxy-containing polymer such as epoxy-containing polyacrylate.

[0126] The epoxide also may comprise an epoxy-adduct. The composition may comprise one or more epoxy-adducts. As used herein, the term “epoxy-adduct” refers to a reaction product of one compound that is at least difunctional and comprises at least one epoxide functional group and at least one other compound that does not include an epoxide functional group. For example, the epoxy-adduct may comprise the reaction product of reactants comprising: (1) an epoxy compound, a polyol, and an anhydride; (2) an epoxy compound, a polyol, and a diacid; or (3) an epoxy compound, a polyol, an anhydride, and a diacid.

[0127] The epoxy compound used to form the epoxy-adduct may comprise any of the epoxy-containing compounds listed above that may be included in the composition.

[0128] The polyol used to form the epoxy-adduct may include diols, triols, tetraols and higher functional polyols. Combinations of such polyols may also be used. The polyols may be based on a polyether chain derived from ethylene glycol, propylene glycol, butylene glycol, hexylene glycol and the like as well as mixtures thereof. The polyol may also be based on a polyester chain derived from ring opening polymerization of caprolactone (referred to as polycaprolactone-based polyols hereinafter). Suitable polyols may also include polyether polyols, polyurethane polyols, polyurea polyols, acrylic polyols, polyester polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, polycarbonate polyols, polysiloxane polyols, and combinations thereof. Polyamines corresponding to polyols may also be used, and in this case, amides instead of carboxylic esters will be formed with the diacids and anhydrides.

[0129] The polyol may comprise a polycaprolactone-based polyol. The polycaprolactone-based polyols may comprise diols, triols or tetraols terminated with primary hydroxyl groups. Commercially avartable polycaprolactone-based polyols include those sold under the trade name Capa™ from Perstorp Group, such as, for example, Capa 2054, Capa 2077A, Capa 2085, Capa 2205, Capa 3031, Capa 3050, Capa 3091 and Capa 4101.

[0130] The polyol may comprise a polytetrahydrofuran-based polyol. The polytetrahydrofuran-based polyols may comprise diols, triols or tetraols terminated with primary hydroxyl groups. Commercially avartable polytetrahydrofuran-based polyols include those sold under the trade name Terathane®, such as Terathane® PTMEG 250 and Terathane® PTMEG 650 which are blends of linear diols in which the hydroxyl groups are separated by repeating tetramethylene ether groups, avartable from Invista. In addition, polyols based on dimer diols sold under the trade names Pripol®, Solvermol™ and Empol®, avartable from Cognis Corporation, or bio-based polyols, such as the tetrafunctional polyol Agrol 4.0, avartable from BioBased Technologies, may also be utilized.

[0131] The anhydride that may be used to form the epoxy-adduct may comprise any suitable acid anhydride known in the art. For example, the anhydride may comprise hexahydrophthalic anhydride and its derivatives (e.g., methyl hexahydrophthalic anhydride); phthalic anhydride and its derivatives (e.g., methyl phthalic anhydride); maleic anhydride; succinic anhydride; trimellitic anhydride; pyromellitic dianhydride (PMDA); 3, 3', 4, 4'-oxydiphthalic dianhydride (ODPA); 3,3',4,4'-benzophenone tetracarboxylic dianhydride (BTDA); and 4,4 '-diphthalic (hcxafluoroisopropylidcnc) anhydride (6FDA).

[0132] The diacid used to form the epoxy-adduct may comprise any suitable diacid known in the art. For example, the diacids may comprise phthalic acid and its derivates (e.g., methyl phthalic acid), hexahydrophthalic acid and its derivatives (e.g., methyl hexahydrophthalic acid), maleic acid, succinic acid, adipic acid, and the like.

[0133] The epoxy-adduct may comprise the reaction product of reactants comprising a diol, a monoanhydride or a diacid, and a diepoxy compound, wherein the mole ratio of diol, monoanhydride (or diacid), and diepoxy compounds in the epoxy-adduct may vary from 0.5:0.8:1.0 to 0.5:1.0:6.0.

[0134] The epoxy-adduct may comprise the reaction product of reactants comprising a triol, a monoanhydride or a diacid, and a diepoxy compound, wherein the mole ratio of triol, monoanhydride (or diacid), and diepoxy compounds in the epoxy-adduct may vary from 0.5:0.8:1.0 to 0.5:1.0:6.0.

[0135] The epoxy-adduct may comprise the reaction product of reactants comprising a tetraol, a monoanhydride or a diacid, and a diepoxy compound, wherein the mole ratio of tetraol, monoanhydride (or diacid), and diepoxy compounds in the epoxy-adduct may vary from 0.5:0.8:1.0 to 0.5:1.0:6.0.

[0136] The epoxide may have an epoxy equivalent weight of at least 90 g / eq, such as at least 140 g / eq, such as at least 188 g / eq, and may have an epoxy equivalent weight of no more than 2,000 g / eq, such as no more than 1,000 g / eq, such as no more than 500 g / eq. The epoxide may have an epoxy equivalent weight of 90 g / eq to 2,000 g / eq, such as 140 g / eq to 1,000 g / eq, such as 188 g / eq to 500 g / eq.

[0137] The epoxide may have at least one functional group that is different from the epoxide functional group(s).

[0138] The curing agent may be Michael acceptor, such as a compound having at least one terminal Michael acceptor group. As used herein, a “Michael acceptor” refers to an activated alkene, such as an alkenyl group proximate to an electron-withdrawing group such as a ketone, nitro, halo, nitrile, carbonyl, or nitro group. Michael acceptors are well known in the art. A “Michael acceptor group” refers to an activated alkenyl group and an electron- withdrawing group. A “Michael acceptor compound” refers to a compound comprising at least one Michaelacceptor group. In non-limiting examples, a Michael acceptor group is selected from a vinyl ketone, a vinyl sulfone, a quinone, an enamine, a ketimine, an aldimine, an oxazolidine, and an acrylate. Other examples of Michael acceptor compounds are disclosed in Mather et al., Prog. Polym. Sci. 2006, 31, 487-53, incorporated herein by reference, and include acrylate esters, acrylonitrile, acrylamides, maleimides, alkyl methacrylates, and cyanoacrylates. Other Michael acceptor compounds include vinyl ketones, a, P-unsaturated aldehydes, vinyl phosphonates, acrylonitrile, vinyl pyridines, azo compounds, P-keto acetylenes and acetylene esters. In other examples, a Michael acceptor group is derived from a vinyl ketone and has the structure of the formula — S(O)2 — C(R)2=CH2, where each R is independently selected from hydrogen, fluorine, and Ci-3 alkyl. In examples, the Michael acceptor compound or Michael acceptor group may include acrylates and acrylics.

[0139] In examples, a Michael acceptor compound comprises a vinyl sulfone including a mixture of different types of vinyl sulfones and / or having different functionalities of Michael acceptor groups. In examples in which the Michael acceptor compound comprises a mixture of vinyl sulfones having different functionalities, the average functionality of the mixture of vinyl sulfones can be 2 to 6, such as 2 to 3. As used herein, the term “average functionality” means the sum of the functionality per component divided by the number of components weighted by their mole ratio.

[0140] Michael acceptor groups are well known in the art. In examples, a Michael acceptor group comprises an activated alkene, such as an alkenyl group proximate to an electronwithdrawing group such as an enone, nitro, halo, nitrile, carbonyl, or nitro group. In certain examples, a Michael acceptor group is selected from a vinyl ketone, a vinyl sulfone, a quinone, an enamine, a ketimine, an aldimine, and an oxazolidine. In examples, each of the Michael acceptor groups may be the same and in other examples, at least some of the Michael acceptor groups may be different.

[0141] As discussed above, the curing agent may comprise an isocyanate. The isocyanate of the present disclosure can be monomeric or polymeric containing one or more isocyanate functional groups (-N=C=O).

[0142] Suitable monomeric isocyanate-containing compounds include p-tolyl isocyanate, hexyl isocyanate, phenyl isocyanate, isocyanate ethyl arylate, methacryloyloxyethyl isocyanate, 3-(triethyoxysilyl)propyl isocyanate.

[0143] Suitable isocyanate-containing compounds that may be used in the compositions described herein may comprise a polyisocyanate. For example, the polyisocyanate may comprise C2-C20 linear, branched, cyclic, aliphatic and / or aromatic poly isocyanates.

[0144] Aliphatic polyisocyanates may include (i) alkylene isocyanates, such as: trimethylene diisocyanate; tetramethylene diisocyanate, such as 1,4-tetramethylene diisocyanate; pentamethylene diisocyanate, such as 1,5 -pentamethylene diisocyanate and 2-methyl-l,5-pentamethylene diisocyanate; hexamethylene diisocyanate (“HDI”), commercially avartable as Demodur XP 2617 (Covestro), such as 1,6-hexamethylene diisocyanate and 2,2,4- and 2,4,4-trimethylhexamethylene diisocyanate, or mixtures thereof; heptamethylene diisocyanate, such as 1,7-heptamethylene diisocyanate; propylene diisocyanate, such as 1,2-propylene diisocyanate; butylene diisocyanate, such as 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, and 1,4-butylene diisocyanate; ethylene diisocyanate; decamethylene diisocyanate, such as 1,10-decamethylene diisocyanate; ethylidene diisocyanate; and butylidene diisocyanate. Aliphatic polyisocyanates may also include (ii) cycloalkylene isocyanates, such as: cyclopentane diisocyanate, such as 1,3-cyclopentane diisocyanate; cyclohexane diisocyanate, such as 1,4-cyclohexane diisocyanate, 1,2-cyclohexane diisocyanate, isophorone diisocyanate (“IPDI”), methylene bis(4-cyclohexylisocyanate) (“HMDI”); and mixed aralkyl diisocyanates such as tetramethylxylyl diisocyanates, such as meta- tetramethylxylylene diisocyanate (commercially avartable as TMXDI® from Allnex SA). Dimers, trimers, oligomers, and polymers of the above-mentioned polyisocyanates also may be used as the cyclotrimer of 1,6 hexamethylene diisocyanate (also known as the isocyanate trimer of HDI, commercially avartable as Desmodur N33OO (Covestro)).

[0145] Aromatic polyisocyanates may include (i) arylene isocyanates, such as: phenylene diisocyanate, such as m-phenylene diisocyanate, p-phenylene diisocyanate, and chlorophenylene 2,4-diisocyanate; naphthalene diisocyanate, such as 1,5 -naphthalene diisocyanate and 1,4-naphthalene diisocyanate. Aromatic polyisocyanates may also include (ii) alkarylene isocyanates, such as: methylene-interrupted aromatic diisocyanates, such as 4,4'-diphenylene methane diisocyanate (“MDI”), and alkylated analogs such as 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, and polymeric methylenediphenyl diisocyanate; toluene diisocyanate (“TDI”), such as 2,4-tolylene or 2,6-tolylene diisocyanate, or mixtures thereof,bitoluene diisocyanate; and 4,4-toluidine diisocyanate; xylene diisocyanate; dianisidine diisocyanate; xylylene diisocyanate; and other alkylated benzene diisocyanatcs.

[0146] Polyisocyanates may also include: triisocyanates, such as triphenyl methane-4,4',4"-triisocyanate, 1,3,5-triisocyanato benzene, and 2,4,6-triisocyanato toluene; tetraisocyanates, such as 4,4'-diphenyldimethyl methane-2,2',5,5'-tetraisocyanate; and polymerized polyisocyanates, such as tolylene diisocyanate dimers and trimers and the like.

[0147] The isocyanate compound may have at least one functional group that is different from the isocyanate functional group(s).

[0148] Suitable vinyls include those described in U. S. Patent No. 8,901,256, at col. 5, 11.15-col. 6, 11. 6, incorporated herein by reference. For example, suitable divinyl ethers include, for example, divinyl ethers having formula (XI):CH2=CH— O— (— R— O)m— CH=CH2, (XI)where R in formula (XI) is selected from a C2-6 n-alkylene group, a C2-6 branched alkylene group, a Ce-8 cycloalkylene group, a Ce-io alkylcycloalkylene group, and -[( — CH2— )p— O — ]q— ( — CH2 — )i —, where p is an integer ranging from 2 to 6, q is an integer ranging from 1 to 5, and r is an integer ranging from 2 to 10. In certain embodiments of a divinyl ether of formula (XI), R is a C2-6 n-alkylene group, a C2-6 branched alkylene group, a C6-8 cycloalkylene group, a Ce-io alkylcycloalkylene group, and in certain embodiments, -[( — CH2— )p— O — ]q— ( — CH2 — )i —. Suitable divinyl ethers include, for example, compounds having at least one oxyalkylene group, such as from 1 to 4 oxyalkylene groups, i.e., compounds in which m in formula (XI) is an integer ranging from 1 to 4. In certain embodiments, m in formula (XI) is an integer ranging from 2 to 4. It is also possible to employ commercially avartable divinyl ether mixtures that are characterized by a non-integral average value for the number of oxyalkylene units per molecule. Thus, m in formula (XI) can also take on rational number values ranging from 0 to 10.0, such as from 1.0 to 10.0, from 1.0 to 4.0, or from 2.0 to 4.0. Examples of suitable divinyl ethers include, for example, divinyl ether, ethylene glycol divinyl ether (EG-DVE) (R in formula (XI) is ethylene and m is 1), butanediol divinyl ether (BD-DVE) (R in formula (XI) is butylene and m is 1), hexanediol divinyl ether (HD-DVE) (R in formula (XI) is hexylene and m is 1), diethylene glycol divinyl ether (DEG-DVE) (R in formula (XI) is ethylene and m is 2), triethylene glycol divinyl ether (R in formula (XI) is ethylene and m is 3), tetraethylene glycol divinyl ether (R in formula (XI) is ethylene and m is 4),cyclohexanedimethanol divinyl ether, polytetrahydrofuryl divinyl ether; trivinyl ether monomers, such as trimethylolpropane trivinyl ether; tctrafunctional ether monomers, such as pentaerythritol tetravinyl ether, and combinations of two or more of such polyvinyl ether monomers. A polyvinyl ether may have one or more pendant groups selected from alkyl groups, hydroxyl groups, alkoxy groups, and amine groups. In certain embodiments, divinyl ethers in which R in formula (XI) is C2-6 branched alkylene may be prepared by reacting a polyhydroxy compound with acetylene. Examples of divinyl ethers of this type include compounds in which R in formula (XI) is an alkyl- substituted methylene group such as — CH(CH)- (for example “PLURIOL®” blends such as PLURIOL®E-200 divinyl ether (BASF Corp., Parsippany, NJ), for which R in formula (XI) is ethylene and m is 3.8) or an alkyl-substituted ethylene (for example CH2CH(CH3) such as “DPE” polymeric blends including DPE-2 and DPE-3 (International Specialty Products, Wayne, NJ)).

[0149] Other useful divinylethers include compounds in which R in formula (XI) is polytetrahydrofuryl (poly-THF) or polyoxyalkylene, such as those having an average of 3 monomer units.

[0150] The composition comprising the silyl-containing polymer may comprise the curing agent in an amount of at least 1 percent by weight based on total weight of the composition, such as at least 5 percent by weight, such as at least 10 percent by weight, such as at least 20 percent by weight. The composition comprising the silyl-containing polymer may comprise the curing agent in an amount of no more than 80 percent by weight based on total weight of the composition, such as no more than 70 percent by weight, such as no more than 60 percent by weight, such as no more than 50 percent by weight. The composition comprising the silyl-containing polymer may comprise the curing agent in an amount of 1 percent by weight to 80 percent by weight based on total weight of the composition, such as 5 percent by weight to 70 percent by weight, such as 10 percent by weight to 60 percent by weight, such as 20 percent by weight to 50 percent by weight.

[0151] The moisture-curable composition comprising the imine may further comprise a curing agent that reacts with the hydrolyzed component, such as a curing agent comprising a molecule comprising an electrophilic functional group, such as an acetoacetate, an acrylate, an epoxide, a Michael acceptor, an isocyanate, or combinations thereof.

[0152] Suitable acrylates, isocyanates, and epoxies useful in the compositions are described above.

[0153] As discussed above, the curing agent may comprise an acetoacetate functional ingredient. As used herein, the term “acetoacetate-functional ingredient” is understood to mean both substituted and non-substituted acetoacetate-functional ingredients. Suitable acetoacetate-functional ingredients include those selected from the group including acetoacetate-functional diluents, acetoacetate-functional oligomers, acetoacetate-functional polymers, and mixtures thereof.

[0154] Suitable acetoacetate-functional ingredients include those having the general chemical formula (XII)R20[OCOCH2COCH2]aR2i(XII)where R2o can be selected from the group including acrylic, polyester, polyether, and urethane polymers or diluents, or any hydroxy-functional polymer that is capable of being functionalized with [OCOCH2COCH2]aR2i, where a can be from 1 to 10, and where R2I can be hydrogen or can be a carbon-containing group having up to 6 carbon atoms.

[0155] Suitable acetoacetate-functional diluents and oligomers include tris acetoacetylated trimethylolpropane (TMP) (avartable, for example, from King Industries of Norwalk, CT under the product name K-Flex such as K-Flex XM-7301), diaacetoacetylated 2-butyl-2-ethyl-l,3-propanediol (BEPD), diacetoacetylated neopentyl glycol (NPG), or any hydroxy-functional diluent that is easily transacetoacetylated, e.g., transesterfied with tertiary butyl acetoacetate (TBAA) with elimination of tertiary butanol, with tributylammonium acetate.

[0156] Suitable acetoacetate-functional polymers include those having an acrylic, polyester, polyether, or urethane chemical backbone. Exemplary acetoacetate-functional acrylic polymers include those avartable, for example, from Akzo Nobel of the Netherlands under the product name Setalux such as Setalux 7202 XX 50; from Guertin Bros., of Canada under the product name CSA such as CSA 582 (85% acetoacetate-functional acrylic polymer having an equivalent weight of 600); and from Guertin Bros., under the product name GPAcryl, e.g., GPAcryl 513, GPAcryl 550, GPAcryl 597, GPAcryl 613, GPAcryl 766; and from Nuplex of Auckland, New Zealand under the product name ACR such as ACR441XD. Suitable acetoacetate-functional polymers include acetoacetate-functional polyester polymers such asthose avartable, for example, from Guertin Bros., under the product name GPEster, for example GPEster 766.

[0157] In addition to those acetoacetate-functional polymers described above, any hydroxyl-functional polymer, be it an acrylic, polyester, urethane, alkyd and the like, that can be converted into an acetoacetate-functional polymer with TBBA are acceptable for use in the compositions of the present disclosure. Example acetoacetate-functional urethane polymers include those that are bonded to acetoacetate, such as urethane diols and urethane triols.

[0158] The composition may comprise the curing agent and / or curing additive in an amount of at least 1 percent by weight based on total weight of the composition, such as at least 5 percent by weight, such as at least 10 percent by weight, such as at least 20 percent by weight. The composition may comprise the curing agent and / or the curing additive in an amount of no more than 80 percent by weight based on total weight of the composition, such as no more than 70 percent by weight, such as no more than 60 percent by weight, such as no more than 50 percent by weight. The composition may comprise the curing agent and / or curing additive in an amount of 1 percent by weight to 80 percent by weight based on total weight of the composition, such as 5 percent by weight to 70 percent by weight, such as 10 percent by weight to 60 percent by weight, such as 20 percent by weight to 50 percent by weight.Additives, Accelerators, and Fillers

[0159] The compositions disclosed herein optionally may comprise an additive. Suitable examples of an additive include a rheology modifier, a reactive diluent, a non-reactive diluent, a dispersant, a tackifier, a thermoplastic polymer, a surface-active agent, a flame retardant, a corrosion inhibitor, a UV stabilizer, a colorant, a tint, a solvent, a plasticizer, an adhesion promoter, an antioxidant, and / or a moisture scavenger.

[0160] As used herein, the term “solvent” refers to a molecule or a compound that is used to lower the viscosity of the resin, volatilizes under ambient conditions, and does not have a reactive functional group capable of reacting with molecules or compounds in a composition.

[0161] As used herein, the term “reactive diluent” refers to a molecule or a compound that is used to lower the viscosity of a resin but that has at least one functional group capable of reacting with a functional group(s) on molecules or compounds in a composition.

[0162] As used herein, the term “non-reactive diluent” refers to a molecule or a compound that is used to lower the viscosity of a resin but that does not have a functional group capable of reacting with a functional group(s) on molecules or compounds in a composition.

[0163] As used herein, the term “plasticizer” refers to a molecule or a compound that does not have a functional group capable of reacting with a functional group(s) on molecules or compounds in a composition and that is added to the composition to decrease viscosity, decrease glass transition temperature (Tg), and impart flexibility.

[0164] The composition may comprise the additive(s), if present at all, in a combined amount of at least 0.1 percent by weight based on total weight of the composition, such as at least 1 percent by weight. The composition may comprise the additive(s), if present at all, in a combined amount of no more than 30 percent by weight based on total weight of the coating composition, such as no more than 20 percent by weight. The composition may comprise the additive(s), if present at all, in a combined amount of 0.1 percent by weight to 30 percent by weight based on total weight of the composition, such as at least 1 percent by weight to 20 percent by weight.

[0165] Any accelerator capable of accelerating a reaction of the hydrolysable component with water and / or the curing agent compound may be used in the present composition. Suitable accelerators that may be used in accordance with the present disclosure thus include for example thiazoles, thiurams, sulfenamides, guanidines, dithiocarbamates, xanthates, thioureas, aldehydeamines, and combinations of any of the foregoing. Examples of suitable thiazoles include bis(2-benzothiazole) disulfide (MBTS), 2-mercaptobenzothiazole (MBT), and the zinc salt of mercaptobenzothiazole (ZMBT). Examples of suitable thiurams include tetramethyl thiuram monosulfide, tetramethyl thiuram disulfide (TMTD), tetraethyl thiuram disulfide, tetrabutyl thiuram disulfide, dipentamethylene thiuram hexasulfide, dicyclohexamethylene thiuram disulfide, diisopropyl thiuram disulfide, bis(morpholinothiocarbonyl) sulfide, tetramethyl thiuram monosulfide (TMTM), dipentamethylene thiuram tetrasulfide (DPTT), and compounds having the structure (R)2N-C(=S)-SX-C(=S)-N(R)2 where each R can be Ci-6 alkyl and x is an integer from 1 to 4, and combinations of any of the foregoing. Examples of suitable sulfonamides include N-cyclohexyl-2-benzothiazol sulfonamide, tertbutyl-2-benzothiazolsulfenamide (TBBS), dicyclohexyl-2-benzothiazolsulfenamide (DCBS), and combinations of any of the foregoing. Examples of suitable guanidines include diphenylguanidine (DPG), N, N’ -diorthotolyl guanidine (DOTG), compounds having the structure R-NH-C(=NH)-NH-R where each R is selected from Ci-6 alkyl, phenyl and toluoyl, and combinations of any of the foregoing. Examples of suitable dithiocarbamates include zinc dialkyl dithiocarbamates such as dimethyl- dithiocarbamate (ZDMC), diethyl-dithiocarbamate (ZDEC) and dibutyl-dithiocarbamate (ZDBC), other metal or ammonium salts of dithiocarbamoic acid, compounds having the structure Zn(-S-C(=S)-N(R)2) where each R is selected from Ci-6 alkyl, phenyl and toluoyl, and combinations of any of the foregoing. Examples of suitable xanthates include zinc salts of xanthic acid. Examples of suitable thioureas include ethylenethiourea (ETU), dipentamethylene thiourea (DPTU), dibutyl thiourea (DBTU), and compounds having the structure R-NH-C(=S)-NH-R where each R is selected from Ci-6 alkyl, phenyl and toluoyl, and combinations of any of the foregoing. Examples of suitable aldehydeamines include condensation products of aldehydes and amines, such as aniline, ammoniac or their derivates and also butyraldehyde, crotonylaldehyde or formaldehyde such as butyraldehydeaniline and tricrotonylidenetetramine, and combinations of any of the foregoing. Examples of other suitable cure accelerators include triazines and sulfides or metallic and amine salts of dialkyldithiophosphoric acids and dithiophosphates such as triazines and sulfides or metallic and amine salts of dialkyldithiophosphoric acids, and combinations of any of the foregoing.Examples of non- sulfur-containing polysulfide cure accelerators include tetramethyl guanidine (TMG), di-o-tolyl guanidine (DOTG), sodium hydroxide (NaOH), water, and amines. Examples of amines include quaternary amines, tertiary amines, cyclic tertiary amines, or secondary amines.

[0166] The accelerator may be a metal-based compound such as tin-based compounds such as dibutyltin dilaurate, dibutyltin dioctanoate, dibutyltin bis(2-ethylhexanoate), dibutyltin diacetate, and dibutyltin bis(acetylacetonate); zinc-based compounds such as zinc bis(2-ethylhexanoate); bismuth-based compounds such as bismuth neodecanoate and bismuth Tris(2-ethylhexanoate); zirconium-based compounds such as zirconium(IV) acetylacetonate; and titanium-based compounds such as tetraisopropyl orthotitanate and titanium(IV) oxyacetylacetonate.

[0167] The accelerator may be an amine-based catalyst such as trimethylamine; tributylamine; N, N-bis(N, N-dimethyl-2-aminoethyl)methylamine; N, N-dimethylcyclohexylamine; N-methylmorpholine; N-ethylmorpholine; piperidine; piperazine;pyrrolidine; homopiperazine; 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine; 1,4,5,6-tetrahydropyrimidine; 1,8-diazabicyclo[5.4.0]undec-7-ene; 1,5,7-triazabicyclo[4.4.0]dec-5-ene; 7-methyl-l,5,7-triazabicyclo[4.4.0]dec-5-ene; 1,5-diazabicyclo[4.3.0]non-5-ene; 6-(dibutylamino)-l,8-diazabicyclo(5,4,0)undec-7-ene; 1,4-diazabicyclo[2.2.2]octane; 7-azabicyclo[2.2.1]heptane; N, N-dimethylphenylamine; 4,5-dihydro-lH-imidazole; and guanidine-based catalysts such as guanidine, dimethylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, phenylguanidine, diphenylguanidine, butylbiguanide, 1-o-tolylbiguanide, 1-phenylbiguanide, 1-methyl-3-nitroguanidine, 1,8-bis(tetramethylguanidino)-naphthalene, and N, N, N', N'-tetramethyl-N"-[4-morpholinyl(phenylimino)methyl]guanidine.

[0168] The accelerator may be an inorganic acid such as, for example, sulfonic acid, p-toluene sulfonic acid, n-butylphosphoric acid, hydrochloric acid, nitric acid, or the like. The accelerator may also be an organic acid, such as, for example, formic acid, citric acid, acetic acid, and triflic acid, or the like.

[0169] Other suitable accelerators include free radical catalysts. Suitable free radical catalysts include, for example, azo compounds, for example azobisnitriles such as azo(bis)isobutyronitrile (AIBN); organic peroxides such as benzoyl peroxide and t-butyl peroxide; and inorganic peroxides such as hydrogen peroxide. The reaction may also be affected by irradiation with ultraviolet light either with or without a cationic photo-initiating moiety. Ionic catalysis methods, using either inorganic or organic bases, e.g., triethylamine, also yield useful materials.

[0170] Other suitable accelerators include organometallic catalysts. Suitable organometallic catalysts are useful for the purpose of further accelerating the curing rate of the composition into a protective film coating over a broad temperature range. In certain use applications calling for ambient temperature cure of the composition, the organometallic catalyst is also useful for providing accelerated cure rates at such ambient temperature cure conditions. Suitable catalysts include those having the general formulawhere R5 and Re are each selected from the group consisting of alkyl, aryl, and alkoxy groups having up to eleven carbon atoms, and where R7 and Rs arc each selected from the same groups as R5 and Re, or from the group consisting of inorganic atoms such as halogens, sulphur or oxygen. Example catalysts include organotin materials such as dibutyl tin dilaurate, dibutyl tin diacetate, and organotitanates.

[0171] The composition may comprise the accelerator, if present at all, in an amount of at least 0.01 percent by weight based on the total weight of the composition, such as at least 1 percent by weight. The composition may comprise the accelerator, if present at all, in an amount of no more than 30 percent by weight based on the total weight of the composition, such as no more than 10 percent by weight. The composition may comprise the accelerator, if present at all, in an amount of 0.01 percent to 30 percent by weight based on the total weight of the composition, such as 1 percent to 10 percent by weight.

[0172] The composition may comprise a filler. Suitable examples of filler useful in the composition include aluminum hydroxide, mica, wollastonite, calcium carbonate, glass microspheres, clay, or combinations thereof.

[0173] The composition may comprise the filler(s), if present at all, in a combined amount of at least 0.1 percent by weight based on total weight of the composition, such as at least 1 percent by weight. The composition may comprise the filler(s), if present at all, in a combined amount of no more than 30 percent by weight based on total weight of the composition, such as no more than 20 percent by weight. The composition may comprise the filler(s), if present at all, in a combined amount of 0.1 percent by weight to 30 percent by weight based on total weight of the composition, such as at least 1 percent by weight to 20 percent by weight.Compositions

[0174] The composition may have a total solids content of at least 40% by weight based on total weight of the composition, such as at least 60% by weight, such as at least 80% by weight, such as 100% by weight based on total weight of the composition. The composition may have a total solids content of 40% by weight to 100% by weight based on total weight of the composition, such as 60% by weight to 100% by weight, such as 80% by weight to 100% by weight. As used herein, “total solids” refers to the non-volatile content of the composition, i.e.,materials which will not volatilize when heated to 110°C at standard atmospheric pressure (101325 Pa) for 60 minutes.

[0175] The composition may be substantially free, or essentially free, or completely free, of a photopolymerizable initiator.

[0176] The composition may be formulated as a sealant composition, an adhesive composition, a gap filler composition, a pottant composition, a prepreg, and / or a liquid shim composition.

[0177] The composition may be formulated as a composition suitable for molding, casting, extrusion, and / or machining.

[0178] The composition may be formulated as a one-component composition, a two-component composition, or a higher-component composition.

[0179] As used herein, a “IK” or “one-component” composition, is a composition in which all the ingredients may be premixed and stored at ambient conditions and wherein the reactive components do not readily react at ambient or slightly thermal conditions such as greater than ambient temperature and less than 60°C. One-component compositions may cure upon exposure to EMR and / or may react at an accelerated rate upon exposure to EMR compared to a cure rate in the absence of EMR. In the absence of such exposure, the composition will remain largely uncured.

[0180] The compositions disclosed herein may be formulated as a IK composition comprising, consisting essentially of, or consisting of a hydrolysable component and optionally a photothermally active material, a curing agent, an accelerator, an additive, and / or a filler.

[0181] As used herein, the term “two-component” or “2K” refers to a composition in which the reactive components readily associate to form an interaction or react to form a bond (physically or chemically), i.e., cure, without activation from an external energy source, such as at ambient or slightly thermal conditions, when mixed. One of skill in the art understands that the two components of the composition are stored separately from each other and mixed just prior to application of the composition. Two-component compositions may be exposed to EMR as described herein. As used herein, “reactive components” refer to components of the final composition containing hydrolysable components.

[0182] The compositions disclosed herein may be formulated as a 2K composition comprising, or consisting essentially of, or consisting of: a first component comprising, orconsisting essentially of, or consisting of a hydrolysable component; and a second component comprising a curing agent. The first component and / or the second component may further comprise a photothermally active material, an accelerator, an additive, and / or a filler. The first and second components may be mixed immediately prior to use.

[0183] The composition may be agitated manually or mechanically to homogenize the ingredients. Volumetric mixers or automated blending devices may be used to homogenize multi-component systems.

[0184] Optionally, the non-hydrolysable component(s) of the two-component compositions (i.e., the curing agent) may comprise water.

[0185] The hydrolysable component of the two-component compositions and optionally the photothermally active material may be packaged in a moisture- sealed container to substantially prevent curing. The hydrolysable component is stable under conditions substantially free of moisture and at ambient temperatures. When the moisture-sealed container is unsealed, the composition may be exposed to moisture which promotes curing of the composition to form a coating or the like.

[0186] When the moisture-sealed container is unsealed and the composition is applied to a substrate, the composition may be exposed to moisture which promotes curing of the composition to form a coating as described in more detart below.

[0187] The components of a two-component composition may be mixed and provided as a pre-mixed frozen composition (PMF). PMFs may be packaged, for example, in a cartridge, a cartridge and plunger, a syringe, or may be supplied as a tape, a cap, or any preformed geometry. PMFs may be cured by external factors, such as EMR. In examples, the PMF may be stored at temperatures of -100°C to -15°C, such as -100°C to -25°C, such as -100°C to -40°C, such as -75°C to -15°C, such as -75°C to -25°C, such as -75°C to -40°C, to inhibit curing. When applying the composition to the substrate, the composition may be exposed to EMR to initiate cure of the composition. As used herein, the term “inhibit,” when used with respect to curing, refers to restraining, impeding, slowing or interfering with a particular reaction or function. This can be accomplished in a number of ways, for example, controlling the environment to which the composition is exposed, such as limiting the composition’s exposure to ambient conditions.Methods and Cured Coatings

[0188] Disclosed herein are methods of curing any of the compositions described above.

[0189] The compositions may be applied alone or as part of a system that can be deposited in a number of different ways onto a number of different substrates. Accordingly, disclosed herein are methods for treating a substrate comprising, consisting essentially of, or consisting of contacting a surface of the substrate with any of the compositions disclosed herein and exposing the composition to a EMR generated by a laser and / or an LED as described above. The composition can be applied to the surface of a substrate in any number of different ways by depositing, applying, or contacting the composition to a substate surface to form a coating thereon, non-limiting examples of which include extruding, pressing, grouting, caulking, spreading, brushing, rolling, troweling, dipping, spraying including airless spraying, high volume low pressure systems, electrostatic systems, coil coating, spin coating, and the like. Optionally, the substrate may be attached to a moveable mount or stage.

[0190] Compositions may be applied in different environments such as a spray booth, a hangar, a paint shop, or a clean room based on need to protect the composition from airborne contaminants. Spray booths can be maintained to keep constant temperature and humidity. Enclosures may be used in hangar operations to help with cleanliness. Coating repair or application may take place in remote locations lacking booths, hangars, or portable enclosures.

[0191] 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.

[0192] 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 hydrolysable component to EMR with a ramp from ambient to a temperature setpoint of at least 80°C and then held at the temperature setpoint of at least 80°C for at least 5 minutes to cure the composition.

[0193] The methods may comprise exposing the compositions to EMR at an intensity of at least 0.01 W / cm2, such as at least 0.1 W / cm2, such as at least 0.2 W / cm2. The methods may comprise exposing the compositions to EMR at an intensity of no more than 108W / cm2, such as no more than 10 W / cm“, such as no more than 10 W / cm, such as no more than 10 W / cm,such as no more than 15 W / cm2, such as no more than 12 W / cm2. The methods may comprise exposing the compositions to EMR at an intensity of 0.01 W / cm2to 108W / cm2, such as 0.1 W / cm2to 106W / cm2, such as 0.1 W / cm2to 104W / cm2, such as 0.1 W / cm2to 102W / cm2, such as 0.1 W / cm2to 15 W / cm2, such as 0.2 W / cm2to 12 W / cm2.

[0194] The composition may be cured as described herein to form a coating, such as a sealant, an adhesive, a gap filler, a pottant, a prepreg, a liquid shim, an article, and / or a part.

[0195] 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.

[0196] The methods disclosed herein may further comprise coating the substrate surface with a coating composition in addition to the composition disclosed herein. That is, the methods may further comprise treating the substrate surface with a pretreatment composition and / or coating the substrate surface with an electrodepositable coating composition, a primer coating composition, a basecoat coating composition, a topcoat coating composition, an adhesion promoter, and the like, as understood by those skilled in the art of substrate protection. That is, “contacting a surface of the substrate” encompasses contacting a surface of a substrate that has been treated with other coatings, as described herein.

[0197] 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.

[0198] 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.

[0199] 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 beadded to control bond thickness. Exposure to EMR may be performed prior to or following the addition of the second substrate to form a joint.

[0200] The methods disclosed herein may cure compositions to make an article or a pre-molded part such as a seal cap, a gasket, an O-ring, a shim, a washer, a grommet, a spacer, a cushion, a mating material, a flange, and / or a plug. As used herein, the term “pre-molded part” refers to apart that has been formed from a composition into a predetermined shape and cured to retain that shape. Although the parts are referred to herein as being “pre-molded”, the parts can be made by any suitable method, such as molding. The coatings and pre-molded parts made by the methods disclosed herein have the ability, when cured, to resist atmospheric conditions such as moisture and temperature and at least partially block the transmission of materials such as water, water vapor, fuel, solvents, liquids, and / or gases.

[0201] 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.

[0202] 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.

[0203] The methods disclosed herein may be performed using a robotically guided laser and / or LED.

[0204] 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.

[0205] It was surprisingly discovered that the methods disclosed herein may cure a composition and may accelerate cure compared to the same composition cured under ambient conditions.

[0206] 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 80°C for at least 5 minutes. The methods disclosed herein may comprise a dual cure method wherein the composition is exposed to EMR to achieve a tack-free surface and thereafter the composition may continue to cure through dark cure. The compositions disclosed herein may achieve a tack-free surface at least 30 minutes following the exposure to the EMR, while the composition may cure to achieve desired physical properties, such as Shore A hardness at least 24 hours after the exposure to EMR, such as at least 96 hours after the exposure to EMR. “Tackiness” may be evaluated using the fingerprint test, which may consist of touching the coating with a gloved finger following exposure to EMR and assessing the tackiness or stickiness of the formed coating. If the gloved finger does not stick to the coating, then the coating may be called “tack-free” at that time point, and if the gloved finger sticks to the coating, was sticky, and / or left a residue on the glove after exposure to EMR, then the coating may be called “tacky.”

[0207] It also 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 following exposure to the EMR held at a temperature setpoint of at least 80°C for at least 5 minutes. The methods may result in a coating having similar mechanical properties, such as Shore A hardness and adhesion, to compositions cured under ambient 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 10, such as at least 15, such as at least 20. 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 20, such as at least 30, such as at least 35, such as at least 40. For example, the methods disclosed herein may result in a coating having a Shore A hardness, measured at least 96 hours after the exposure to the EMR and according to ASTM D2240-15, of at least 30, such as at least 35, such as at least 40, such as at least 45. For example, the methods disclosed herein may result in a coating having cohesive farture similar to that of coatings cured in a conventional oven. That is, the coating was cohesive. As used herein, “cohesive farture” and like terms refer to a coating that, when tested for delamination from thepanel, leaves a portion of the coating on the panel (as compared to “adhesive farture,” 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.

[0208] 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.

[0209] 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 80°C for at least 5 minutes was less than 450 J / cm2, such as less than 400 J / cm2, such as less than 350 J / cm2, such as less than 300 J / cm2.

[0210] 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 80°C for at least 5 minutes was reduced by at least 3%, such as by at least 10%, such as by at least 15%, such as by at least 20%, such as by at least 25%, such as by at least 30% compared to total energy density required to ramp and maintain the same composition that did not include a photothermally active material at the temperature setpoint for at least 5 minutes.

[0211] These results surprisingly and unexpectedly demonstrated that exposure of a composition to EMR generated by a laser may provide a tack-free surface following termination of the exposure to EMR without negatively impacting dark cure or mechanical properties of theresulting coating. Thus, it was surprisingly and unexpectedly demonstrated that curing the compositions disclosed herein by exposure to EMR generated by a laser and / or an LED may be advantageous to achieve cure on demand, maintained dark cure mechanisms, and 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 hereinSubstrates

[0212] 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 rart 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.

[0213] “Vehicle” as used herein refers to in its broadest sense all types of vehicles, such as, but not limited to, cars, trucks, buses, tractors, harvesters, heavy duty equipment, vans, golf carts, motorcycles, bicycles, rartcars, 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.

[0214] 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 ofmanufacture, 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, trarters, and any metal structure that is exposed to a corrosive environment.

[0215] 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.

[0216] 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 carbonfiber-epoxy composites, 3-D printed polymers and composites, synthetic fibers and the like, such as those avartable as Kevlar® materials. The shape of the substrate can be in the form of a sheet, plate, bar, rod, or any shape desired.

[0217] 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

[0218] For purposes of this detarted description, it is to be understood that the disclosure may assume alternative variations, except where expressly specified to the contrary.

[0219] The numerical values set forth in the examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard variation found in their respective testing measurements.

[0220] 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.

[0221] As used herein, “including,” “containing” and like terms are understood in the context of this application to be synonymous with “comprising” and are therefore open-ended and do not exclude the presence of additional undescribed or unrecited elements, materials, or ingredients. As used herein, “consisting of’ is understood in the context of this application to exclude the presence of any unspecified element, material, or ingredient. As used herein, “consisting essentially of’ is understood in the context of this application to include the specifiedelements, materials, or ingredients and those that do not materially affect the basic and novel characteristics of what is being described.

[0222] 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.

[0223] As used herein, the terms “on,” “onto,” “applied on,” “applied onto,” “formed on,” “deposited on,” “deposited onto,” and the like mean formed, overlaid, deposited, or provided on, but not necessarily in contact with, a substrate surface. For example, a composition “applied onto” a substrate surface does not preclude the presence of one or more intervening coating layers or films of the same or different composition located between the composition and the substrate surface.

[0224] As used herein, a “composition” refers to a solution, mixture, or dispersion that is capable of forming a coating on a substrate surface. “Coating” as used herein includes films, layers, and the like.

[0225] As used herein, a “sealant composition” refers to a composition that forms a sealant in its cured state.

[0226] As used herein, the term “sealant” refers to a coating that has the ability to resist atmospheric conditions, such as moisture and temperature, and at least partially block the transmission of materials, such as water, fuel, liquids, and gases. The compositions disclosed herein may be useful, for example, as aerospace sealants and linings for fuel tanks.

[0227] As used herein, a “gap filler composition” refers to a composition that forms a gap filler in its cured state.

[0228] 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.

[0229] As used herein, an “adhesive composition” refers to a composition that forms an adhesive in its cured state.

[0230] As used herein, an “adhesive” refers to a coating that produces a load-bearing joint.

[0231] As used herein, a “pottant composition” refers to a composition that, when cured, forms a pottant.

[0232] As used herein, a “pottant” refers to an encapsulant.

[0233] As used herein, a “pre-preg” refers to a composition pre-impregnating reinforcement fibers prior to cure.

[0234] As used herein, a “liquid shim composition” refers to a composition that, when cured, forms a liquid shim.

[0235] As used herein, a “liquid shim” refers to a coating that eliminates gaps between substrate surfaces.

[0236] As used herein, “ambient” conditions generally refer to room temperature (e.g., 25°C) and humidity conditions or temperature and humidity conditions that are typically found in the area in which the composition is applied to a substrate, e.g., at 10°C to 40°C and 5% to 80% relative humidity,, while “slightly thermal” conditions are temperatures that are 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).

[0237] As used herein, the term “cure,” “curing,” and similar terms mean that the components that form the composition begin to crosslink (i.e., interact and / or react) to form a coating or a bond or a surface that is tack-free. In the case of a 2K composition, the composition begins to cure when the components of the composition are mixed, resulting in the reaction of the reactive functional groups of the components of the composition and / or the physical interaction of the components of the composition.

[0238] As used herein, “tack free” means a material that is dry to the touch on the surface and that does not leave a residue when touched.

[0239] As used herein, the term “curing agent” means any reactive material that can be added to a composition to cure the composition.

[0240] As used herein, the term “weight average molecular weight” or “(Mw)” means the weight average molecular weight (Mw) as determined by gel permeation chromatography (GPC) using polystyrene standards for calibration.

[0241] As used herein, “polymer” refers to oligomers, homopolymers, and copolymers.

[0242] As used herein, “hydrolysable component” refers to a component having at least one terminal or sidechain hydrolysable group. As used herein, “hydrolysable group” refers to a group that is capable of undergoing hydrolysis.

[0243] As used herein, the “epoxy equivalent weight” is determined by dividing the Mw of the epoxy compound by the average number of epoxide groups present in the epoxy compound.

[0244] As used herein, a dash (“ — ”) that is not between two letters or symbols is used to indicate a point of bonding for a substituent or between two atoms. For example, — CONH2 refers to an amide functional group that is bonded to another chemical moiety through the carbon atom.

[0245] As used herein, “alkoxy” refers to a — OR group where R is alkyl or aromatic as defined herein. Non-limiting examples of alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, and n-butoxy.

[0246] 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.

[0247] As used herein, unless indicated otherwise, the term “substantially free” means that a particular material is not purposefully added to a mixture or composition, respectively, and is present only as an impurity in a trace amount of less than 0.05% by weight based on a total weight of the mixture or composition, respectively. As used herein, unless indicated otherwise, the term “essentially free” means that a particular material is present only in an amount of less than 0.01 % by weight based on a total weight of the mixture or composition, respectively. As used herein, unless indicated otherwise, the term “completely free” means that a mixture or composition, respectively, does not comprise a particular material, i.e., the mixture or composition comprises 0% by weight of such material.

[0248] In view of the foregoing description the present disclosure thus relates to the following Aspects 1 to 121 without being limited thereto.

[0249] 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 hydrolysable component.

[0250] 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 hydrolysable component.

[0251] Aspect 3. The method of aspect 1 or aspect 2, wherein the EMR comprises visible light and / or near infrared light.

[0252] 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.

[0253] Aspect 5. The method of any of the preceding aspects, wherein the EMR comprises a wavelength of at least 960 nm.

[0254] 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.

[0255] 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.

[0256] 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.

[0257] 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.

[0258] Aspect 10. The method of any of the preceding aspects, wherein the EMR comprises a wavelength of 960 nm to 985 nm.

[0259] 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.

[0260] Aspect 12. The method of any of the preceding aspects, wherein the EMR is directional.

[0261] Aspect 13. The method of any of the preceding aspects, wherein the EMR comprises monochromatic light and / or polychromatic light.

[0262] Aspect 14. The method of any of the preceding aspects, wherein the EMR is coherent.

[0263] Aspect 15. The method of any of aspects 1 and 3 to 14, wherein the laser and / or the LED is defocused.

[0264] Aspect 16. The method of any of the preceding aspects, wherein the laser generates diffuse EMR, divergent EMR, and / or collimated EMR.

[0265] 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.

[0266] 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.

[0267] 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.

[0268] 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.

[0269] 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.

[0270] 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.

[0271] 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.

[0272] Aspect 24. The method of any of the preceding aspects, wherein the laser and / or the LED comprises adaptive optics such as optics to tartor focal intensity and / or a wide area distribution of the EMR.

[0273] 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.

[0274] 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.

[0275] 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.

[0276] 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.

[0277] Aspect 29. The method of any of the preceding aspects, wherein the composition further comprises a photothermally active material.

[0278] Aspect 30. The method of aspect 29, wherein the photothermally active material comprises carbon black, a solubilized pigment, and / or copper phthalocyanine.

[0279] Aspect 31. The method of aspect 29 or aspect 30, wherein the photothermally active material is soluble and / or in a particulate form.

[0280] 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.

[0281] 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.

[0282] 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 0.05 percent by weight based on total weight of the composition.

[0283] 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.

[0284] 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 based on total weight of the composition.

[0285] 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.

[0286] Aspect 38. The method 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 15 percent by weight based on total weight of the composition, such as 1 percent by weight to 10 percent by weight.

[0287] Aspect 39. The method of any of the preceding aspects, wherein the hydrolysable component comprises a silane-containing component having a hydrolysable group, a silyl-containing component having a hydrolysable group, and / or an imine-containing component comprising a hydrolysable group.

[0288] Aspect 40. The method of any of the preceding aspects, wherein the composition comprises the hydrolysable component in an amount of at least 1 percent by weight based on total weight of the composition, such as at least 5 percent by weight.

[0289] Aspect 41. The method of any of the preceding aspects, wherein the composition comprises the hydrolysable component in an amount of at least 10 percent by weight based on total weight of the composition, such as at least 15 percent by weight.

[0290] Aspect 42. The method of any of the preceding aspects, wherein the composition comprises the hydrolysable component in an amount of at least 30 percent by weight based on total weight of the composition.

[0291] Aspect 43. The method of any of the preceding aspects, wherein the composition comprises the hydrolysable component in an amount of no more than 99.9999 percent by weight based on total weight of the composition, such as no more than 98.99 percent by weight.

[0292] Aspect 44. The method of any of the preceding aspects, wherein the composition comprises the hydrolysable component in an amount of no more than 80 percent by weight based on total weight of the composition, such as no more than 70 percent by weight.

[0293] Aspect 45. The method of any of the preceding aspects, wherein the composition comprises the hydrolysable component in an amount of no more than 60 percent by weight based on total weight of the composition.

[0294] Aspect 46. The method of any of aspects 1 to 40 and 43, wherein the composition comprises the hydrolysable component in an amount of 1 percent by weight to 99.9999 percent by weight based on total weight of the composition, such as 5 percent by weight to 98.99 percent by weight.

[0295] Aspect 47. The method of any of aspects 1 to 41, 43, 44, and 46, wherein the composition comprises the hydrolysable component in an amount of 10 percent by weight to 80 percent by weight based on total weight of the composition, such as 15 percent by weight to 70 percent by weight.

[0296] Aspect 48. The method of any of the preceding aspects, wherein the composition comprises the hydrolysable component in an amount of 30 percent by weight to 60 percent by weight based on total weight of the composition.

[0297] Aspect 49. The method of any of the preceding aspects, wherein the composition further comprises a curing agent comprising a functional group capable of reacting with a functional group of the hydrolysable component after hydrolysis, such as a curing agent comprising an electrophilic functional group.

[0298] Aspect 50. The method of any of aspects 1 to 48, wherein the composition further comprises a curing agent such as an acetoacetate, an acrylate, an epoxide, a Michael acceptor, an isocyanate, a silanol, a polyol, a thiol, a polythiol, and / or a mercaptan terminated polyether.

[0299] Aspect 51. The method of aspect 49 or aspect 50, comprising the curing agent in an amount of at least 1 percent by weight based on total weight of the composition, such as at least 5 percent by weight.

[0300] Aspect 52. The method of any of aspects 49 to 51, comprising the curing agent 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.

[0301] Aspect 53. The method of any of aspects 49 to 52, comprising the curing agent 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.

[0302] Aspect 54. The method of any of aspects 49 to 53, comprising the curing agent in an amount of no more than 70 percent by weight based on total weight of the composition, such as no more than 60 percent by weight.

[0303] Aspect 55. The method of any of aspects 49 to 54, comprising the curing agent in an amount of no more than 50 percent by weight based on total weight of the composition.

[0304] Aspect 56. The method of any of aspects 49 to 51 and 53, comprising the curing agent in an amount of 1 percent by weight to 90 percent by weight based on total weight of the composition, such as 1 percent by weight to 80 percent by weight.

[0305] Aspect 57. The method of any of aspects 49 to 51, 53, 54, and 56, comprising the curing agent in an amount of 5 percent by weight to 70 percent by weight based on total weight of the composition, such as 10 percent by weight to 60 percent by weight.

[0306] Aspect 58. The method of any of aspects 49 to 57, comprising the curing agent in an amount of 20 percent by weight to 50 percent by weight based on total weight of the composition.

[0307] Aspect 59. The method of any of any of the preceding aspects, wherein the hydrolysable group comprises formula (I):Zn_ l _— Y— X(m-n)wherein when Y-Si. then m-3. n=0, and X-R, wherein R-H, an alkoxy, an acyloxy, or a halogen, and wherein Z= an organo-carbon chain, an alkyl, a branched alkyl, or a substituted alkyl; and wherein when Y=S, then m=l, n=l, Z=R, wherein R=hydrogen, an organo-carbon chain, an alkyl, a branched alkyl, or a substituted alkyl, and X=silyl group containing an alkyl group, a branched alkyl group, a substituted alkyl group, or a phenyl group; and wherein when Y=C, then m=l, n=0 and X=a nitrogen; wherein the silyl group has formula (II):S—Si—R3? R5(II)wherein R3, R4, and R5are each independently selected from a Ci-6 n-alkyl group, a Ci-6 branched alkyl group, a substituted Ci-6 n-alkyl group, and a phenyl group and may be the same or different.

[0308] Aspect 60. The method of any of the preceding aspects, wherein the hydrolysable component is substantially free, essentially free, or completely free of a silicone-containing species having the formula (III):wherein R16, R17 and R18 are independently selected from the group consisting of H, alkyl, aryl, cycloalkyl, alkoxy, aryloxy, hydroxyalkyl, alkoxyalkyl and hydroxy-alkoxyalkyl groups containing up to six carbon atoms, and where R19 is selected from the group consisting of H and alkyl and aryl groups containing up to six carbon atoms, and "n" is greater than 1.

[0309] Aspect 61. The method of any of aspects 39 to 60, wherein the silane-containing polymer comprises a polyester, a polyether, a polyurethane, a polyurea, a polyisocyanate, a polyolefin, and / or a poly(meth)acrylate.

[0310] Aspect 62. The method of any of aspects 39 to 61, wherein the silane-containing polymer comprises any of formula (IV) to (VI).

[0311] Aspect 63. The method of any of aspects 39 to 62, comprising the silane-containing polymer in an amount of at least 10 percent by weight based on total weight of the composition, such as at least 15 percent by weight.

[0312] Aspect 64. The method of any of aspects 39 to 63, comprising the silane-containing polymer in an amount of no more than 99.9999 percent by weight based on total weight of the composition, such as no more than 80 percent by weight.

[0313] Aspect 65. The method of any of aspects 39 to 64, comprising the silane-containing polymer in an amount of 10 percent by weight to 99.9999 percent by weight based on total weight of the composition, such as 15 percent by weight to 80 percent by weight.

[0314] Aspect 66. The method of any of aspects 39 to 65, wherein the silyl-containing polymer comprises a sulfur-containing polymer such as a substituted polythioether, a substituted polysulfide, a substituted thiol ester, and / or a substituted thiol polyacrylate.

[0315] Aspect 67. The method of any of aspects 39 to 66, wherein the silyl-containing polymer may comprise at least two groups per molecule having the formula (IX).

[0316] Aspect 68. The method of any of aspects 39 to 67, wherein the silyl-containing polymer has an average functionality of 2 to 6.

[0317] Aspect 69. The method of any of aspects 39 to 68, wherein the composition comprises the silyl-containing polymer in an amount of at least 1.5 percent by weight based on total weight of the composition, such as at least 30 percent by weight.

[0318] Aspect 70. The method of any of aspects 39 to 69, wherein the composition comprises the silyl-containing polymer in an amount of no more than 98.99 percent by weight based on total weight of the composition, such as no more than 60 percent by weight.

[0319] Aspect 71. The method of any of aspects 39 to 70, wherein the composition comprises the silyl-containing polymer in an amount of 1.5 percent by weight to 98.99 based on total weight of the composition, such as 30 percent by weight to 60 percent by weight.

[0320] Aspect 72. The method of any of aspects 39 to 71, wherein the imine comprises a ketimine and / or an aldimine.

[0321] Aspect 73. The method of any of aspects 39 to 72, wherein the imine comprises any of formulae (X) to (XXXV).

[0322] Aspect 74. The method of any of aspects 39 to 73, wherein the composition comprises the imine in an amount of at least 1.5 percent by weight based on total weight of the composition, such as at least 30 percent by weight.

[0323] Aspect 75. The method of any of aspects 39 to 74, wherein the composition comprises the imine in an amount of no more than 98.99 percent by weight based on total weight of the composition, such as no more than 60 percent by weight.

[0324] Aspect 76. The method of any of aspects 39 to 75, wherein the composition comprises the imine in an amount of 1.5 percent by weight to 98.99 percent by weight based on total weight of the composition, such as 30 percent by weight to 60 percent by weight.

[0325] Aspect 77. The method of any of the preceding aspects, wherein the composition further comprises: (i) an additive such as a rheology modifier, a reactive diluent, a non-reactive diluent, a dispersant, a tackifier, a thermoplastic polymer, a surface-active agent, a flame retardant, a corrosion inhibitor, a UV stabilizer, a colorant, a tint, a solvent, a plasticizer, an adhesion promoter, an antioxidant, and / or a moisture scavenger; (ii) an accelerator; and / or (iii) a filler.

[0326] Aspect 78. The method of any of the preceding aspects, wherein the composition has a total solids content of at least 40 percent by weight based on total weight of the composition, such as at least 60 percent by weight.

[0327] Aspect 79. The method of any of the preceding aspects, wherein the composition has a total solids content of at least 80 percent by weight based on total weight of thecomposition.

[0328] Aspect 80. The method of any of aspects 1 to 78, wherein the composition has a total solids content of 40 percent by weight to 100 percent by weight based on total weight of the composition, such as 60 percent by weight to 100 percent by weight.

[0329] Aspect 81. The method of any of aspects 1 to 78 and 80, wherein the composition has a total solids content of 80 percent by weight to 100 percent by weight based on total weight of the composition.

[0330] Aspect 82. The method of any of aspects 1 to 77, wherein the composition has a total solids content of 100 percent by weight based on total weight of the composition.

[0331] Aspect 83. The method of any of the preceding aspects, wherein the composition is substantially free, essentially free, or completely free of a photopolymerizable initiator.

[0332] Aspect 84. The method of any of the preceding aspects, wherein the composition is formulated as a sealant composition, an adhesive composition, a gap filler composition, a pottant composition, a prepreg, and / or a liquid shim composition.

[0333] Aspect 85. The method of any of the preceding aspects, wherein the composition is formulated as a composition suitable for molding, casting, and / or extrusion.

[0334] Aspect 86. The method of any of the preceding aspects, wherein the composition is formulated as a IK composition, a 2K composition, a higher-component composition, and / or a PMF.

[0335] Aspect 87. The method of any of the preceding aspects, comprising applying the composition to a surface of a substrate, such as by extruding, pressing, grouting, caulking, spreading, brushing, rolling, troweling, dipping, and / or spraying.

[0336] Aspect 88. The method of any of the preceding aspects, wherein the composition is exposed to the EMR for at least 5 minutes.

[0337] Aspect 89. 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.

[0338] Aspect 90. 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.

[0339] Aspect 91. 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.

[0340] Aspect 92. 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.

[0341] Aspect 93. The method of any of the preceding aspects, wherein the composition is exposed to the EMR at an intensity of no more than 15 W / cm2, such as no more than 12 W / cm2.

[0342] Aspect 94. The method of any of aspects 1 to 89 and 91, 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.

[0343] Aspect 95. The method of any of aspects 1 to 89, 91, 92, and 94, 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.

[0344] Aspect 96. The method of any of aspects 1 to 89 and 91 to 95, 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.

[0345] Aspect 97. The method of any of aspects 87 to 96, comprising cleaning and / or deoxidizing the surface of the substrate.

[0346] Aspect 98. The method of any of aspects 87 to 97, comprising coating the substrate surface with a coating composition in addition to the composition such as a pretreatment composition, an electrodepositable coating composition, a primer coating composition, a basecoat coating composition, and / or a topcoat coating composition.

[0347] Aspect 99. The method of any of the preceding aspects, wherein the substrate comprises a fixed structure.

[0348] Aspect 100. The method of any of aspects 87 to 99, comprising applying the composition to a damaged portion of the surface of the substrate.

[0349] Aspect 101. The method of aspect 100, 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.

[0350] Aspect 102. The method of any of the preceding aspects, wherein a temperature of the composition is maintained at a temperature setpoint of at least 80°C.

[0351] Aspect 103. The method of any of aspects 87 to 102, 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.

[0352] Aspect 104. The method of any of aspects 87 to 103, further comprising contacting a surface of a second substrate to the composition such that the composition is between the surface of the substrate and the second substrate.

[0353] Aspect 105. The method of any of the preceding aspects, further comprising dark curing the composition.

[0354] Aspect 106. The method of aspect 105, wherein the dark curing is for a period of at least 24 hours, such as at least 96 hours.

[0355] Aspect 107. The method of any of the preceding aspects, wherein a rate of curing the composition is accelerated compared to a rate of curing the composition under ambient conditions.

[0356] Aspect 108. The method of any of the preceding aspects, wherein a total energy density of less than 450 J / cm2is required to cure the coating, such as less than 400 J / cm2.

[0357] Aspect 109. The method of any of the preceding aspects, wherein a total energy density of less than 350 J / cm2is required to cure the coating, such as less than 300 J / cm2.

[0358] Aspect 110. The method of any of aspects 29 to 109, wherein a total energy density required to cure the composition was reduced by at least 3% 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%.

[0359] Aspect 111. The method of any of aspects 29 to 110, 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%.

[0360] Aspect 112. The method of any of aspects 29 to 111, wherein a total energy density required to cure the composition was reduced by at least 25% compared to a total energy density required to cure a composition that did not comprise the photothermally active material, such as reduced by at least 30%.

[0361] Aspect 113. The method of any of the preceding aspects, wherein a temperature of the substrate following exposure to the EMR is below a heat deflection temperature of the substrate.

[0362] Aspect 114. A substrate comprising a coating formed from the composition cured by the method of any of the preceding aspects.

[0363] Aspect 115. The substrate of aspect 114, wherein the coating comprises a sealant, an adhesive, a gap filler, a pottant, a prepreg, and / or a liquid shim.

[0364] Aspect 116. The substrate of aspect 114 or aspect 115, wherein the cured coating has a Shore A hardness of at least 10 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 15.

[0365] Aspect 117. The substrate of any of aspects 114 to 116, wherein the cured coating has a Shore A hardness of at least 20 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 65.

[0366] Aspect 118. The substrate of any of aspects 114 to 117, wherein the cured coating has a Shore A hardness of at least 20 measured according to ASTM D2240-15 at 24 hours after the exposure to EMR, such as a Shore A hardness of at least 30.

[0367] Aspect 119. The substrate of any of aspects 114 to 118, wherein the cured coating has a Shore A hardness of at least 35 measured according to ASTM D2240-15 at 24 hours after the exposure to EMR, such as a Shore A hardness of at least 40.

[0368] Aspect 120. The substrate of any of aspects 114 to 119, wherein the cured coating has a Shore A hardness of at least 20 measured according to ASTM D2240-15 at 96 hours after the exposure to EMR, such as a Shore A hardness of at least 30.

[0369] Aspect 121. The substrate of any of aspects 114 to 120, wherein the coating is cohesive.

[0370] Illustrating the disclosure are the following examples, which, however, are not to be considered as limiting the disclosure to their detarts.EXAMPLESTable 1: Compositions 1 to 71MS Polymer S303H commercially avartable from Kaneka.2Plasticizer commercially avartable from LANXESS.3Nano calcium carbonate (filler) commercially avartable from Specialty Minerals Inc.4Micron-sized calcium carbonate (filler) commercially avartable from Huber Engineered Materials.' Titanium dioxide commercially avartable from The Chemours Company.6Micronised amide wax rheology modifier commercially avartable from Arkema.7Vinyltrimethoxysilane-based moisture scavenger commercially avartable from Evonik.8Diamino functional silane commercially avartable from Evonik.9Acid catalyst commercially avartable from Nitto Kasei Co., Ltd.10Amine catalyst commercially avartable from Momentive.11Monarch 120 Carbon Black (photothermally active material) commercially avartable from Cabot.12Copper phthalocyanine (photothermally active material) commercially avartable from Penn Color, Inc.

[0371] The compositions were prepared and mixed using a Hauschild Speedmix DAC mixer, model 600.1 FVZ. A master batch was prepared at 30x scale by combining and mixing all the listed components in Table I except the catalyst, filler, and photothermally active material on the DAC mixer for 45 seconds at 500 rpm. Then the catalyst, filler, and photothermallyactive material were added and mixed on the DAC mixer for an additional 45 seconds at 500 rpm. The mixture was inspected and mixed manually with a spatula to ensure homogeneity.

[0372] At the application stage, 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 Aluminum substrates. Each aluminum substrate was treated with a CDX395 (prepared according to manufacturer’s instructions; a pretreatment commercially avartable from PPG Industries, Inc.) as follows: (i) rinsed in acetone for 1 min, (ii) rinsed in deionized water for 1 min, (iii) soaked in CDX395 bath equilibrated to 100°F for 1 min, and (iv) rinsed in deionized water for 1 min. Cure of the samples was monitored for 96 hours, at which point final hardness was measured for all samples, as determined by Shore A hardness measured according to ASTM D2240-15.

[0373] 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). Samples 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 80°C and then held at 80°C for 5 minutes (30 minutes in the case of Example 7). Shore A hardness was measured after the composition cooled to ambient temperature. Shore A hardness was measured over 96 hours as reported in Table 2.

[0374] Ambient-cured samples. Samples were drawn down on MEK-cleaned and chemically deoxidized 7075-T6 Al substrates and allowed to cure at 25°C for 96 hours, then checked for hardness as described above. Data are reported in Table 3.

[0375] Total Energy Density calculation. Maximum laser output was 4500W. The total energy density was calculated according to Equation 1 disclosed above.

[0376] Samples were drawn down (1” x 2.5” x 0.125”) on MEK-cleaned 7075-T6 Al substrate and allowed to cure for 1 week. Panel adhesion was tested by using a Semco® scraper (P / N 235073) to manually initiate detachment of the sealant from the substrate and then pulling the sealant at a 180° angle. If the coating cleanly delaminated from the panel (i.e., adhesive farture), the result was recorded as “fart.” If the coating left a thin film of material on the panel(i.e., thin-film cohesive farture) or farted cohesively, the result was considered a “pass.” Results are reported in Table 4.Table 2: Total Energy Density and Shore A Hardness Cure Profile Post-Laser ExposureTable 3: Shore A Hardness Cure Profile Under Ambient ConditionsTable 4: Terminal Hardness and Adhesion Testing at 96 h** Shore A Hardness at 96 hr. Data are copied from Table 2 above.*** Shore A Hardness at 96 hr. Data are copied from Table 3 above.**** Shore A Hardness at 96 hr. Data are copied from Table 4 above.

[0377] For each of the Compositions 1 to 7, no significant difference was observed in extent of cure between the laser-irradiated samples and the oven-cured samples as determined by Shore A hardness. Each became tack-free by shore A measurement after its respective heating cycle. The ambient-cure samples were still tacky and did not yield a Shore A measurement when assessed after the same amount of time as the heat-cure samples. By 24 h and 96 h, all samples had reached parity in Shore A hardness. All samples passed the panel adhesion test described above. It was notable that Composition 1, the control, required a greater total energy density in its laser cure cycle compared to Compositions 2 to 7, which contained various amounts of photothermally active material.

[0378] Whereas specific aspects of the disclosure have been described in detart, it will be appreciated by those skilled in the art that various modifications and alternatives to those detarts 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 hydrolysable component.

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

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

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

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

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

7. The method of claim 6, wherein the photothermally active material comprises carbon black and / or copper phthalocyanine.

8. The method of claim 6 or claim 7, wherein the composition comprising 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.

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

10. The method of any of the preceding claims, wherein a total energy density of less than 450 J / cm2is required to cure the coating.

11. The method of any of claims 6 to 10, wherein a total energy density required to cure the composition was reduced by at least 3% compared to a total energy density required to cure a composition that did not comprise the photothermally active material.

12. The method of any of the preceding claims, wherein the composition has a tack-free surface at least 30 minutes following the exposure to the EMR.

13. The method of any of the preceding claims, further comprising dark-curing the composition following the exposing.

14. The method of claim 13, wherein the dark-curing is for a period of time of up to 96 hours.

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

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

17. The method of claim 16, further comprising cleaning, deoxidizing, abrading, and / or pretreating the surface of the substrate prior to the applying.

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

19. The substrate of claim 18, wherein the cured coating has:(a) a Shore A hardness of at least 10 measured according to ASTM D2240-15 following the exposure to EMR and cooling the coating to ambient temperature;(b) a Shore A hardness of at least 20 measured according to ASTM D2240-15 at 24 hours after the exposure to EMR; and / or(c) a Shore A hardness of at least 20 measured according to ASTM D2240-15 at 96 hours after the exposure to EMR.

20. The substrate of claim 18 or claim 19, wherein the coating is cohesive.

Images