Methods of curing thiol-containing 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 includes a thiol-terminated compound and an oxidant. Also disclosed are substrates comprising a coating formed from a composition cured by the disclosed methods.

Description

METHODS OF CURING THIOL-CONTAINING COMPOSITIONSCROSS-REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to U.S. Provisional Application No. 63 / 714,476, filed on October 31, 2024, and entitled “Polysulfide 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 thiol-containing compound using electromagnetic radiation are disclosed.BACKGROUND

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

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

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

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

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

[0008] FIG. 1 is a graph showing the Shore A hardness of cured Composition 2 as a function of time (days) and cured under laser, oven, or ambient conditions.

[0009] FIG. 2 is a graph showing the Shore A hardness of cured Composition 3 as a function of time (days) and cured under laser, oven, or ambient conditions.

[0010] FIG. 3 is a graph showing the Shore A hardness cured Composition 4 as a function of time (days) and cured under laser, oven, or ambient conditions.DETAILED DESCRIPTION

[0011] 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.

[0012] As described in more detail below, the composition may comprise (a) a thiol-terminated compound and (b) an oxidant.Electromagnetic Radiation and Laser

[0013] Exposure of any of the compositions disclosed herein to electromagnetic radiation (“EMR”) may cure the compositions disclosed herein. As used herein, “electromagnetic radiation” refers to a form of energy that includes visible light and near infrared (“nIR”) light. The EMR may be generated by a laser and / or a light emitting diode (“LED”). As used herein, “visible light” refers to EMR with wavelengths in the range of 380 nm to 750 nm which is visible to the human eye. As used herein, “near' infrared light” refers to EMR with wavelengths in the range of greater than 750 nm to 2,500 nm.

[0014] 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.

[0015] 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.

[0016] 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 700 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.

[0017] The EMR may be generated as a continuous wave, a quasi-continuous wave, and / or a pulsed wave. As used herein, “continuous wave,” when used with respect to EMR, refers to a constant, uninterrupted beam of light as long as the laser is powered and having a duty cycle of 100%. As used herein, “quasi-continuous wave,” when used with respect to EMR, refers to a series of pulses of light beams with intervals of no emission and having a duty cycle of greater than 50% to less than 100%. As used herein, “pulsed wave,” when used with respect to EMR, refers to a series of pulses of light beams with a duration of femtoseconds to milliseconds separated by intervals of no emission and having a duty cycle of greater than 0% to 50%. As used herein, “duty cycle” refers to the percentage of time that light is actively emitted by laser during a given period of operation. Duty cycle may be calculated according to the following formula: Duty Cycle (D) = (Pulse Duration) / (Pulse Period) * 100%, where “pulse duration” is the time interval during which the laser emits light in one pulse, wherein “pulse period” is the total time interval of one cycle including the pulse duration plus the off time (when the laser is not emitting light). The person skilled in the art of laser technologies will understandthat the selection of duty cycle impacts thermal management and power output and must be compatible with the cure chemistry and the substrate to which the composition is applied.

[0018] 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.

[0019] 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.

[0020] 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.

[0021] 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.

[0022] 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.

[0023] 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.

[0024] 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).

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] Any suitable laser diode configuration may be used. For example, the laser diode configuration may comprise a single diode, a diode laser bar, and / or a diode laser stack. As used herein, a “single diode” laser refers to a single semiconductor device in which a diode pumped with electrical current creates lasing conditions at the diode’s junction. Single diodes may be electrically connected such that the decline or failure of any one diode does not affect the output of the still-operational diodes. As used herein, a “diode laser bar” refers to an array of single diodes positioned side-by-side on a single semiconductor chip. A diode laser bar may comprise, for example, 10 to 50 emitters spaced apart, such as 100 μm to 200 μm apart, and connected in parallel or in series. As used herein, a “diode laser stack” refers to an assembly of multiple diode laser bars stacked vertically or arranged in arrays. A diode laser stack may comprise, for example, 5 or more diode laser bars, such as up to 20 diodes, such as up to 300 diodes, such as more than 300 diodes.

[0031] The diode laser stack may be coupled, such as pigtail-coupled, to more than one fiber or may be configured as a bundle of fibers. As used herein, “pigtail coupled” refers to a laser diode that is permanently connected to an optical fiber, forming a single unit. Fibers may comprise multi-mode fibers with core diameters of, for example, 100 μm to 600 μm or larger.

[0032] 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.

[0033] Adaptive optics may be used to enhance the capabilities of the laser and / or LED, such as those useful for tailoring focal intensity and wide-area distribution of the EMR.

[0034] A laser and / or an LED may be used to cure coatings over a variety of types of substrate surfaces having a range of surface areas, including a vehicle, such as an automobile, a tractor, a trailer, or an aerospace vehicle, an aerospace structure such as a wing, a skin, and / or a fuselage of an aerospace vehicle, a body in white (that is, the stage before painting in automobile manufacturing in which a car- body's frame has been joined together), an appliance or a part thereof, a roof, a door, a ship, a large and / or fixed object such as a bridge, a building, an offshore 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.

[0035] 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.

[0036] 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.

[0037] EMR may be generated by a portable laser and / or LED, a hand-held laser and / or LED, and / or 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.

[0038] EMR may be generated by a robotically guided laser and / or LED.Thiol-Terminated Compounds

[0039] The composition comprises a thiol- terminated compound. The thiol-terminated compound may be a monomer, a polymer, and / or an oligomer. Suitable thiol-terminated compounds are disclosed in U. S. Patent No. 7,858,703B2, 3:27 to 11:54, incorporated herein by reference. The thiol-terminated compound may comprise a liquid.

[0040] The thiol-terminated compound of the present disclosure may have the structure of Formula (I):HS-R1-SH (I)wherein R1is selected from C2-6 alkanediyl, Ce-s cycloalkanediyl, Ce-io alkanecycloalkanediyl, C5-8 heterocycloalkanediyl, substituted C2-6 alkanediyl, substituted Ce-8 cycloalkanediyl, substituted Ce-io alkanecycloalkanediyl, substituted C5-8 heterocycloalkanediyl and — [(CHR3)P— X]q— (CHR3)t —; where, each R3is selected from hydrogen and methyl; each X is independently selected from O, S, S — S, NH, and N( — CH3); p is an integer from 2 to 6; q is an integer from 1 to 5; and r is an integer from 2 to 10. In examples, each p can independently be 2, 3, 4, 5, or 6. In examples, each p can be the same and can be 2, 3, 4, 5, or 6.

[0041] Further useful dithiols include one or more heteroatom substituents in the carbon backbone, that is, dithiols in which X includes a heteroatom such as O, S, S-S, or another bivalent heteroatom radical; a secondary or tertiary amine group, i.e., — NR6—, where R6is hydrogen or methyl; or another substituted trivalent heteroatom. In an example, X is O or S, and thusexamples, p and r may be equal, and in an example, both have the value of 2.

[0042] 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-butanedi thiol, 2,3-butanedithiol, 1.3-pentanedithiol, 1,5 -pentanedi thiol, 1,6-hexanedithiol, l,3-dimercapto-3-methylbutane, dipentenedimercaptan, ethylcyclohexyldithiol (ECHDT), dimercaptodiethylsulfide, methylsubstituted dimercaptodiethylsulfide, dimethyl-substituted dimercaptodiethylsulfide,dimercaptodioxaoctane, 1,5-dimercapto-3-oxapentane, and mixtures thereof. The polythiol material can have one or more pendant groups selected from lower alkyl groups, lower alkoxy groups, and hydroxyl groups. Suitable alkyl pendant groups include C1-C6linear-alkyl, C3-C6branched alkyl, cyclopentyl, and cyclohexyl.

[0043] Useful dithiols include dimercaptodiethylsulfide (DMDS) (p=2, r=2, q=l, X=S); dimercaptodioxaoctane (DMDO) (p=2, q=2, r=2, X=0); and l,5-dimercapto-3-oxapentane (p=2, r=2, q=l, X=O). It is also possible to use dithiols that include both heteroatom substituents in the carbon backbone and pendant alkyl groups, such as methyl groups. Such compounds include methyl-substituted DMDS, such as HS— CH2CH(CH3)— S— CH2CH2— SH or HS— CH(CH3)CH2 — S — CH2CH2 — SH, and dimethyl substituted DMDS such as HS — CH2CH(CH3)— S— CH(CH3)CH2— SH or HS— CH(CH3)CH2— S— CH2CH(CH3)— SH.

[0044] Two or more different polythiols can be used if desired in the compositions of the present disclosure.

[0045] A thiol-terminated compound useful in the compositions of the present disclosure may have the structure of formula (II):HS— R1— [— S— (CH2)P— O— (— R2— O— )m— (CH2)q— S— R1— ]„— SH (II) wherein R1denotes a C2-10 n-alkanediyl, C2-6 branched alkylene, Ce-s cycloalkylene, or Ce-10 alkylcycloalkylene group, heterocyclic, — [( — CH2)P— X]q— ( — CH2)r; or — [( — CH2)P— X]q— ( — CH2)I — in which at least one — CH2— unit is substituted with a methyl group; R2denotes a C2-10 n-alkylene, C2-6 branched alkylene, C6-8 cycloalkylene, or Ce-14 alkylcycloalkylene group, heterocyclic, — [( — CH2)P— X |q— ( — CH2)r; each X is independently selected from the group consisting of O, S, S-S, and — NR6—; R6denotes H or methyl; m is an independently selected rational number from 1 to 50; and n is an independently selected integer from 1 to 60; p is an independently selected integer from 2 to 6; q is an independently selected integer from 1 to 5; and r is an independently selected integer from 2 to 10. In an example of the foregoing polymer, R1is C2-Ce alkyl and R2is C2-C6 alkyl.

[0046] Polyfunctional thiol-terminated polymers according to the present disclosure may have the formula III:B— {R8CH2CH2— O— (R2— O)mCH2CH2— S— R1— [— S— CH2CH2— O— (R2— O)m— CH2— S— R1],!— SH}zOrB— {R8— S— R1— [— S— CH2CH2— O— (R2— 0)m— CH2— S— R1^— SH}Zwherein B denotes a z-valent residue of a polyfunctionalizing agent, R1, R2, n, and m denote structures and values discussed above with reference to Formula II, R8denotes a residue of a terminal vinyl group or thiol group, and z is an integer from 3 to 6.

[0047] Other suitable thiol-terminated monomers for use in the compositions of the present disclosure include, for example, mercapto-propionates, mercapto-acetates, mercaptoacrylates, and combinations of any of the foregoing.

[0048] Examples of suitable mercapto-propionates for use in the compositions of the present disclosure include pentaerythritol tetra(3-mercapto-propionate) (PETMP), trimethylolpropane tri(3-mercaptopropionate) (TMPMP), glycol di(3-mercaptopropionate) (GDMP), tris[2-(3-mercapto-propionyloxy)ethyl]isocyanurate (TEMPIC), di-pentaerythritol hexa(3-mercaptopropionate) (di-PETMP), tri(3-mercaptopropionate) pentaerythritol, triethylolethane tri-(3-mercaptopropionate), and combinations of any of the foregoing.

[0049] Examples of suitable polymeric thiols for use in the compositions of the present disclosure include ethoxylated trimethylolpropane tri(3-mercaptopropionate), polycaprolactone tetra-3-mercaptopropionate, and combinations thereof.

[0050] Examples of suitable mercapto-acetates for use in the compositions of the present disclosure include pentaerythritol tetramercaptoacetate (PRTMA), trimethylolpropane trimercaptoacetate (TMPMA), glycol dimercaptoacetate (GDMA), ethyleneglycol dimercaptoacetate, di-trimethylolpropane tetramercaptoacetate, and combinations of any of the foregoing.

[0051] Examples of suitable mercapto-acrylates for use in the compositions of the present disclosure include pentaerythritol tetra-acrylate, tris[2-(3-mercaptopropionyloxy)ethyl]isocyanurate, 2,3-di(2-mercaptoethylthio)-1-propane-thiol, dimercaptodiethylsulfide (2,2'-thiodiethanethiol), dimercaptodioxaoctane (2,2'-(ethylenedioxy)diethanethiol, l,8-dimercapto-3,6-dioxaoctane, and combinations of any of the foregoing.

[0052] Suitable thiol-terminated monomers for use in compositions of the present disclosure are commercially available, for example, from Bruno Bock Thiochemicals under the Thiocure® tradename. Suitable thiol-terminated polymers for use in compositions of the presentdisclosure are commercially available, for example, from Toray Industries, Inc. under the Thiokol® LP tradename or from Nouryon under the Thioplast® tradename.

[0053] The thiol-terminated compound may have a weight average molecular weight (Mw) of at least 200 g / mol, such as at least 1,000 g / mol, such as at least 2,000 g / mol, and may have a weight average molecular weight of no more than 10,000 g / mol, such as no more than 8,000 g / mol, such as no more than 6,000 g / mol. The thiol-terminated compound may have a weight average molecular weight of 200 g / mol to 10,000 g / mol, such as 1,000 g / mol to 8,000 g / mol, such as 2,000 g / mol to 6,000 g / mol. 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) in tetrahydrofuran (THF) against polystyrene standards for calibration. For example, GPC determination can be performed using a Waters 2695 separation module with a Waters 410 differential refractometer (RI detector), linear polystyrene standards having molecular weights of from 580 Da to 365,000 Da, THF as the eluent at a flow rate of 0.5 mL / min, and an Agilent PL gel Mixed-C column (300 x 7.5 mm, 5 μm) for separation.

[0054] The composition may comprise the thiol-terminated compound 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 may comprise the thiol-terminated compound in an amount of no more than 99 percent by weight based on total weight of the composition, such as no more than 75 percent by weight. The composition may comprise the thiol-terminated compound in an amount of 20 percent by weight to 99 percent by weight based on total weight of the composition, such as 40 percent by weight to 75 percent by weight.Oxidants

[0055] The composition comprises an oxidant such as an oxidant comprising activated manganese dioxide, sodium dichromate, zinc chromate, and / or alkaline dichromate. As used herein, “activated manganese dioxide” refers to manganese dioxide exposed to alkaline chemical treatment to increase reactivity or to enhance performance compared to manganese dioxide not treated by such alkaline chemical treatment. The manganese dioxide may optionally be thermally treated to remove impurities or affect crystallinity, surface area and other physicochemical properties. The manganese dioxide may also consist of a variety of particle sizes such as nanoparticles through particles greater than one micron. The oxidant may polymerize the thiol-terminated polymers of the present disclosure to rubbery solids by oxidizingthe thiol functional group of the thiol-terminated compound to form sulfur-sulfur bonds. For example, a mechanism of cure may comprise 2 -RSH + (O) -^RSSR + H2O.

[0056] The composition may comprise the oxidant in an amount of at least 0.01 percent by weight based on total weight of the composition, such as at least 0.1 percent by weight, such as at least 0.5 percent by weight. The composition may comprise the oxidant in an amount of no more than 15 percent by weight based on total weight of the composition, such as no more than 10 percent by weight. The composition may comprise the oxidant in an amount of 0.01 percent by weight to 15 percent by weight based on total weight of the composition, such as 0.1 percent by weight to 10 percent by weight, such as 0.5 percent by weight to 10 percent by weight.Cure Additives

[0057] The curing rate may be modified by the addition of a cure additive, such as a cure retarder or an accelerator. As used herein, the term “cure retarder” means a substance that decreases the rate of a chemical reaction in comparison to the same reaction in the absence of the cure retarder. As used herein, the term “accelerator” means a substance that increases the rate or decreases the activation energy of a chemical reaction in comparison to the same reaction in the absence of the accelerator. An accelerator may be either a “catalyst,” that is, without itself undergoing any permanent chemical change, or may be reactive, that is, capable of chemical reactions and includes any level of reaction from partial to complete reaction of a reactant.

[0058] Compositions may comprise a poly sulfide cure retarder or a combination of poly sulfide cure retarders. A poly sulfide cure retarder can comprise an acid such as a fatty acid, an organic acid, an inorganic acid, a fatty acid salt, or combinations thereof. Examples of suitable poly sulfide cure retarders include phenylphosphonic acid and itaconic acid.

[0059] The composition optionally may comprise any accelerator capable of accelerating a reaction of the thiol-terminated compound and optionally the oxidant.

[0060] Suitable accelerators include, for example, a thiazole, a thiuram, a sulfenamide, a guanidine, a dithiocarbamate, a xanthate, a thiourea, an aldehydeamine, 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), dipcntamcthylcnc thiuram tctrasulfidc (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 sulfenamides include A^-cyclohexyl-2-benzothiazolsulfenamide, tertbutyl-2-benzothiazolsulfenamide (TBBS), dicyclohexyl-2-benzothiazolsulfenamide (DCBS), and combinations of any of the foregoing. Examples of suitable guanidines include diphenyl guanidine (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 dithiocarbamic 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 ethylene thiourea (ETU), dipentamethylene thiourea (DPTU), dibutyl thiourea (DBTU), and compounds having the structure R-NH-C(=S)-NH-R where each R is selected from C1-6 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, ammonia, or their derivatives 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 dialkyldi thiophosphoric 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 bases such as amines. Examples of amines include quaternary amines, tertiary amines, cyclic tertiary amines, or secondary amines.

[0061] If present at all, the composition may comprise the cure retarder and / or the accelerator in an amount of at least 0.01 percent by weight based on total weight of the composition, such as at least 0.1 percent by weight. If present at all, the composition may comprise the cure retarder and / or the accelerator in an amount of no more than 7 percent byweight based on total weight of the composition, such as no more than 4 percent by weight. If present at all, the composition may comprise the cure retarder and / or the accelerator in an amount of 0.01 percent by weight to 7 percent by weight based on total weight of the composition, such as 0.1 percent by weight to 4 percent by weight.Additives

[0062] The disclosed compositions optionally may comprise an additive. Such additives include a rheology modifier, a reactive diluent, a dispersant, a tackifier, a thermoplastic polymer, a surfactant, a flame retardant, a corrosion inhibitor, a UV stabilizer, a colorant, a tint, a solvent, a plasticizer, an adhesion promoter, and / or a moisture scavenger.

[0063] 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.

[0064] 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.

[0065] As used herein, the term “plasticizer” refers to a molecule or a compound that does not have a functional group capable of reacting with 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.

[0066] The coating 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 coating composition, such as at least 1 percent by weight. The coating 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 coating 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 coating composition, such as at least 1 percent by weight to 20 percent by weight.Filler

[0067] 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.

[0068] The composition may comprise the filler(s), if present at all, in a combined amount of at least 0.1 percent by weight based on total weight of the composition, such as at least 1 percent by weight. The composition may comprise the filer(s), if present at all, in a combined amount of no more than 30 percent by weight based on total weight of the composition, such as no more than 20 percent by weight. The composition may comprise 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

[0069] 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, and may have a total solids content of no more than 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 (1 atm) for 60 minutes.

[0070] The composition may be formulated as a liquid. As used herein, “liquid” refers to a material having a viscosity of no more than 5,000 Pas at 25 °C as measured by parallel plate rheology with a plate diameter of 25 mm, a gap of 1.0 mm, and a shear rate of Is"1.

[0071] The composition may be substantially free, essentially free, or completely free of a photopolymerizable initiator.

[0072] The composition may be formulated as a one-component composition, a two-component composition, or a higher-component composition.

[0073] 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 reaction rate in the absence of EMR. In the absence of such exposure, the composition willremain largely uncured. As used herein, “reactive components” refer to components of the final composition containing thiol functional groups.

[0074] The compositions disclosed herein may be formulated as a IK composition comprising, consisting essentially of, or consisting of a thiol-terminated compound and an oxidant. The IK composition optionally may further comprise an additive, a cure additive, and / or a filler as described above. The IK composition may comprise, consist essentially of, or consist of a thiol-terminated compound and an oxidant comprising activated manganese dioxide, and optionally an additive, a cure additive, and / or a filler.

[0075] 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.

[0076] The compositions disclosed herein may be formulated as a 2K composition comprising, consisting essentially of, or consisting of: a first component comprising, consisting essentially of, or consisting of a thiol-terminated compound; and a second component comprising, consisting essentially of, or consisting of an oxidant. The first component and / or the second component optionally may further comprise a cure additive, a filler, and / or an additive as described above. The 2K composition may comprise, consist essentially of, or consist of: a first component comprising, consisting essentially of, or consisting of a thiol-terminated compound; a second component comprising, consisting essentially of, or consisting of an oxidant comprising activated manganese dioxide; and optionally an additive, a cure additive, and / or a filler. The first and second components may be mixed immediately prior to use.

[0077] The compositions of a two-component composition may be mixed and provided as pre-mixed frozen compositions (PMF). PMFs may be packaged, for example, in a cartridge, a cartridge and plunger, a syringe, or may be supplied as a tape, a cap, or any preformed geometry. For example, the PMF may be packaged in a cartridge assembly described below. 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, suchas -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.

[0078] The composition may be formulated as a sealant composition, an adhesive composition, a gap filler composition, a pottant composition, a prepreg, a liquid shim composition, and / or a composition suitable for molding, casting, extrusion, and / or machining.Dispensing Technologies

[0079] Those skilled in the art are aware that dispensing gun technologies include but are not limited to manual, pneumatic, battery powered, automated meter mix and others. Cartridge based systems exist in a variety of configurations which vary the number of cartridges, cartridge sizes, mix tips, dwell time, mix ratios and other properties based on requirements. The sealant may also be packaged into a Semkit® assembly such as those available from PPG Industries, Inc.

[0080] Also disclosed herein is a coating application kit. The compositions disclosed herein may be packaged in a cartridge assembly used for mixing the various components (i.e., the first, the second, etc., components) of the composition. The cartridge assemblies may be configured to hold a two-component composition. The two-component composition may be any of the compositions described above. For example, one of the first component or the second component may comprise a thiol-containing component, and the other of the first component and the second component may comprise an oxidant.

[0081] The cartridge assembly may comprise a cartridge and an injector. The cartridge may contain the first component of the composition. The injector may contain the second component of the composition. The cartridge and the injector may be structured and arranged to allow the second component to flow into the cartridge to form a coating composition.

[0082] The cartridge assembly may comprise a cartridge comprising a first compartment containing the first component of the composition, a second compartment containing the second component of the composition, and a barrier separating the first compartment and the secondcompartment. A piercer may be structured and arranged to break the barrier to allow the first component and the second component to flow together to form the composition.

[0083] The kit further comprises instructions for exposing the composition to EMR generated by a laser and / or an LED to cure the composition, as described herein.Methods and Cured Coatings

[0084] Disclosed herein are methods of curing any of the compositions described above.

[0085] The compositions may be applied alone or as pail of a system that can be deposited in a number of different ways onto a number of different substrates. Accordingly, disclosed herein are methods for treating a substrate comprising, consisting essentially of, or consisting of contacting a surface of the substrate with any of the compositions disclosed herein and exposing the composition to EMR generated by a laser and / or an LED as described above. The composition can be applied to the surface of the substrate in any number of different ways by depositing, applying, or contacting the composition to the substate surface to form a coating thereon, non-limiting examples of which include extruding, pressing, grouting, caulking, spreading, brushing, rolling, troweling, dipping, spraying, and the like.

[0086] In some instances, the composition may be packaged in various dispensing devices known to those skilled in the art, such as a cartridge assembly (as described above) used for mixing the various components (i.e., the first, the second, etc., components) of the composition. Once discharged from the coating application kit, the composition may be applied to a substrate surface using any of the methods described above and may be cured as described herein.

[0087] Compositions may be applied in different environments such as a spray booth, a hangar, a paint shop, or a clean room based on the need to protect the composition from airborne contaminants. Spray booths can be maintained to keep constant temperature and humidity. Enclosures may be used in hangar operations to help with cleanliness. Coating repair or application may take place in remote locations lacking booths, hangars, or portable enclosures.

[0088] The method comprises exposing the composition to EMR generated by a laser and / or an LED to cure the coating 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.

[0089] The method may comprise exposing the composition comprising thiol-containing compound and the oxidant to EMR for at least 20 minutes to cure the composition. For example, the method may comprise exposing the composition comprising the thiol-containing compound and the oxidant to EMR with a ramp from ambient to a temperature setpoint of at least 110°C and then held at the temperature setpoint of at least 110°C for at least 20 minutes to cure the composition.

[0090] The method may comprise exposing the composition comprising the thiol-containing compound and the oxidant to EMR at an intensity of at least 0.01 W / cm2, such as at least 0.1 W / cm2, such as 0.2 W / cm2. The method may comprise exposing the composition comprising the thiol-containing compound and the oxidant to EMR at an intensity of no more than 108W / cm2, such as no more than 106W / cm2, such as no more than 104W / cm2, such as no more than 102W / cm2, such as no more than 15 W / cm2, such as no more than 12 W / cm2. The method may comprise exposing the composition comprising the thiol-containing compound and the oxidant 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.

[0091] 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, and / or an article.

[0092] The methods disclosed herein may cure coating 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.

[0093] The methods disclosed herein may further comprise cleaning and / or deoxidizing the substrate surface. Suitable methods of cleaning include solvent-wiping, alkaline cleaning,mechanical cleaning and / or abrasion, ultrasonic cleaning, plasma cleaned or etched, and the like, as understood by those skilled in the art of substrate protection.

[0094] The methods disclosed herein may further comprise coating the substrate surface with a coating composition in addition to the disclosed composition. That is, the methods may further comprise treating the substrate surface with a pretreatment composition and / or coating the substrate surface with an electrodepositable coating composition, a primer coating composition, a basecoat coating composition, a topcoat coating composition, 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.

[0095] 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.

[0096] 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.

[0097] The method optionally may further comprise contacting a surface of a second substrate to the composition such that the composition is between the first substrate and the second substrate. For example, the composition may be applied to either one or both of the substrate materials such that the composition is positioned between the first and the second substrates. In examples, the substrates may be aligned, and pressure and / or spacers may be added to control bond thickness. Exposure to EMR may be performed prior to or following the addition of the second substrate to form a joint.

[0098] The methods disclosed herein may include “flashing” or a “dwell time” prior to exposing the composition to EMR, such as to remove volatile components from the composition, such as solvents including organic solvents and / or water, or to allow for flow and leveling. The flash or dwell time may be at ambient or elevated temperature. In methods that include an elevated temperature flash step or dwell time, the heating of the applied composition may be from conventional means such as a convection oven or from exposure to EMR. As used herein, “flashing” refers to exposing the composition to conditions under which solvents begin toevaporate. As used herein, “dwell time” refers to an amount of time a composition is in contact with a substrate surface prior to further processing or drying.

[0099] 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.

[0100] 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.

[0101] The methods disclosed herein may be performed using a robotically guided laser and / or LED.

[0102] 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.

[0103] The methods disclosed herein may cure a composition. For example, 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 following exposure to the EMR held at a temperature setpoint of at least 110°C for at least 20 minutes. The methods may accelerate cure relative to the same coating composition cured under ambient conditions. As discussed in more detail below, the methods may result in a coating having similar mechanical properties, such as Shore A hardness, to compositions cured under ambient conditions.

[0104] The methods disclosed herein may impart useful dual cure properties to the coating compositions disclosed herein. For example, curing may be initiated by exposure of a composition to EMR and / or following exposure of the composition to EMR. Such dual cure mechanisms may be useful for curing compositions applied to geometries and configurations where it is not possible to directly expose a composition to EMR. For example, a portion ofthe composition can be exposed to the EMR thereby accelerating cure in the exposed areas, with cure continuing in these areas via a dark cure curing mechanism when the exposure to EMR is stopped. Dark curing mechanisms will also occur in portions of the composition that are not exposed to EMR. As used herein, “dark cure” refers to the ability of the components of a composition to cure in the absence of exposure to EMR. Dark cure may occur over at least 1 day, such as over at least 3 days, such as over at least 4 days, such as over at least 7 days, such as over at least 14 days, such as over at least 21 days, such as over at least 56 days, such over at least 112 days. Surprisingly, while exposure to EMR accelerated cure of the composition, it did not negatively affect the dark curing mechanism.

[0105] In other examples, it may be advantageous to accelerate cure of the composition to be tack-free on its surface, thereby facilitating productivity by shortening the wait time before a coating may be touched or further processed. “Tackiness” may be evaluated using the fingerprint test, which may consist of touching the 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.” For example, “tackiness” may be evaluated at least 30 minutes up to no more than 336 hours of exposing the composition to EMR and cooling the composition to ambient temperature, such as evaluated at least 1 hour following termination of the exposure to the EMR, such as at least 6 hours following the termination, such as at least 12 hours following the termination, such as at least 24 hours following the termination, such as at least 48 hours following the termination, such as at least 72 hours following the termination, such as at least 96 hours following the termination, such as at least 120 hours following the termination, such as at least 144 hours following the termination, such as at least 168 hours following the termination.

[0106] The methods disclosed herein may comprise a dual cure method wherein the coating composition is exposed to EMR to achieve a tack-free surface and thereafter the composition may continue to cure through dark cure. The compositions disclosed herein may achieve a tack-free surface as described above following the exposure of the coating composition to the EMR, while the composition may dark cure under ambient conditions to achieve desired physical properties, such as Shore A hardness, 72 hours following the exposure, such as 96 hoursfollowing the exposure, such as 168 hours following the exposure, such as 336 hours following the exposure.

[0107] It was surprisingly and unexpectedly discovered that exposure of the compositions disclosed herein to EMR generated by a laser and / or an LED cured the coating composition to at least a tack-free surface following exposure to the EMR for at least 20 minutes, including ramp to temperature setpoint and hold time at temperature setpoint, such as a temperature setpoint of 110°C. For example, exposure of the coating compositions disclosed herein to EMR generated by a laser and having a wavelength of 900 nm to 1,080 nm, such as 960 nm to 985 nm, cured the coating composition to at least a tack-free surface following exposure to the EMR for a 30 second ramp from ambient to 110°C and held at 110°C for 20 minutes.

[0108] It was surprisingly and unexpectedly discovered that exposure of the compositions disclosed herein to EMR generated by a laser resulted in a cured coating faster than ambient-cured samples, as demonstrated by Shore A hardness values measured after the composition cooled to ambient temperature following the laser exposure. Exposure of the compositions disclosed herein to EMR generated by a laser and having a wavelength of 900 nm to 1,080 nm, such as 960 nm to 985 nm, resulted in a coating having a Shore A hardness, measured according to SAE AS5127 / 1D once the coating temperature returned to ambient temperature following the exposure (i.e., at least 40 minutes of the termination of the exposure to the EMR), of at least 25, such as at least 30.

[0109] It also was surprisingly and unexpectedly discovered that exposure of the compositions disclosed herein to EMR generated by a laser and having a wavelength of 900 nm to 1,080 nm, such as 960 nm to 985 nm, resulted in continued cure (i.e., dark cure) in the days following laser exposure as demonstrated by the continued increase in Shore A hardness at least 72 hours following the termination of exposure of the composition to EMR, such as at least 96 hours following the termination of exposure of the composition to EMR, such as at least 168 hours following the termination of exposure of the composition to EMR, such as at least 336 hours following the termination of exposure of the composition to EMR. Exposure of the compositions disclosed herein to EMR generated by a laser LED and having a wavelength of 900 nm to 1,080 nm, such as 960 nm to 985 nm, resulted in a cured composition having a Shore A hardness, measured according to SAE AS5127 / 1D, at least 72 hours to 96 hours following termination of the exposure to EMR of at least 40, such as at least 45, such as at least 50.Exposure of the compositions disclosed herein to EMR generated by a laser and having a wavelength of 900 nm to 1,080 nm, such as 960 nm to 985 nm, resulted in a cured coating having a Shore A hardness, measured according to SAE AS5127 / 1D, at least 168 hours following termination of the exposure of at least 15, such as at least 20, such as at least 25, such as at least 30, such as at least 35, such as at least 40, such as at least 45, such as at least 50. Exposure of the compositions disclosed herein to EMR generated by a laser and having a wavelength of 900 nm to 1,080 nm, such as 960 nm to 985 nm, resulted in a cured coating having a Shore A hardness, measured according to SAE AS5127 / 1D, at least 336 hours following termination of the exposure of at least 20, such as at least 25, such as at least 30, such as at least 35, such as at least 40, such as at least 45, such as at least 50, such as at least 55.

[0110] Additionally, it was surprisingly and unexpectedly discovered that, 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 setpoint (defined in the Examples) was reduced compared to the total energy density required to ramp and maintain the same composition that did not include an oxidant 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 setpoint of 110°C for 30 minutes was less than 2,000 J / cm2, such as less than 1,500 J / cm2, such as less than 1,200 J / cm2, such as less than 1,100 J / cm2.

[0111] It was also surprisingly and unexpectedly discovered that, 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 compositions disclosed herein at a temperature setpoint of 110°C for 30 minutes was reduced by at least 30%, such as by at least 40%, such as by at least 50% compared to total energy density required to ramp and maintain the same composition that did not include an oxidant at the temperature setpoint.

[0112] These results surprisingly and unexpectedly demonstrated that exposure of a composition to EMR generated by a laser may provide a tack-free surface at least 40 minutes following termination of the exposure to EMR without negatively impacting dark cure or mechanical properties of the resulting coating. Thus, it was surprisingly and unexpectedly demonstrated that curing the compositions disclosed herein by exposure to EMR generated by a laser and / or an LED may be advantageous to achieve cure on demand, maintained dark curemechanisms, and a mechanically robust coating. As used herein, “cure on demand” refers to a composition whose cure rate and / or degree of cure, as measured by Shore A hardness as a function of time, for example, can be accelerated by exposure of the composition to EMR having a wavelength of 900 nm to 1,080 nm, such as 960 nm to 985 nm, as disclosed herein.Substrates

[0113] Substrates useful for the methods disclosed herein may be selected from a wide variety of substrates and combinations thereof. Non-limiting examples of substrates include vehicles including automotive substrates, industrial substrates, marine substrates and components such as ships, vessels, and on-shore and off-shore installations, storage tanks such as fuel tanks, packaging substrates, pressurized cabins, architectural substrates, aircraft and aerospace components, batteries and battery components, bus bars, metal wires, electrical and aviation equipment, structural joints and rivets, caps, copper or aluminum conductors, nickel conductors, wood flooring and furniture, fasteners, coiled metals, heat exchangers, vents, an extrusion, roofing, walls, wheels, grates, belts, conveyors, grain or seed silos, wire mesh, bolts or nuts, a screen or grid, HVAC equipment such as environmental control systems, frames, tanks, cords, wires, a rail car, furniture, appliances, apparel, a bulkhead, pipes, transformers, toolboxes, grills, medical equipment, doors, windows, a well, cabinets, pylons, electronics and electronic components including housings and circuit boards, glass, sports equipment, including golfballs, large and / or fixed objects such as stadiums, buildings, bridges, containers such as a food and beverage containers, and the like.

[0114] “Vehicle” as used herein refers to in its broadest sense all types of vehicles, such as, but not limited to, cars, trucks, buses, tractors, harvesters, heavy duty equipment, vans, golf carts, motorcycles, bicycles, railcars, subway cars, airplanes, drones, VTOLs, helicopters, ships, vessels, boats of all sizes and the like. A vehicle can include civilian, commercial and military aircraft or land vehicles, such as those listed above and those used in land-based defense (tanks, armored vehicles, and the like). A vehicle can include autonomous and / or unmanned vehicles.

[0115] It will also be appreciated that the substrates of the present disclosure can form a part of a structure. The coating compositions of the present disclosure can be used in any article of manufacture, such as a vehicle or a structure. “Structure” as used herein refers to a any part of a building, stadium, bridge, transportation infrastructure, oil rig, oil platform, water tower, power line tower, support structures, wind turbines, storage tanks, nuclear plants, walls, piers, docks,levees, dams, shipping containers, trailers, and any metal structure that is exposed to a corrosive environment.

[0116] 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.

[0117] Non-metallic substrates include polymeric, plastic, polyester, polyolefin, polyamide, cellulosic, polystyrene, polyacrylic, poly(ethylene naphthalate), polypropylene, polyethylene, nylon, ethylene vinyl alcohol (EVOH), polylactic acid, other “green” polymeric substrates, poly(ethyleneterephthalate) (PET), polycarbonate, engineering polymers such as poly(etheretherketone) (PEEK), polycarbonate acrylobutadiene styrene (PC / ABS), polyamide, wood, veneer, wood composite, particle board, medium density fiberboard, cement, stone, glass, paper, cardboard, textiles, leather both synthetic and natural, composite substrates such as fiberglass composites or carbon fiber composites such as fiberglass -epoxy composites or carbon fiber-epoxy composites, 3-D printed polymers and composites, synthetic fibers and the like, such as those available as Kevlar® materials. The shape of the substrate can be in the form of a sheet, plate, bar, rod, or any shape desired.

[0118] The substrate may comprise a bare substrate or the substrate may undergo various treatments prior to application of the coating 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 coating composition. The substrate can be treated using any of the previously described methods prior to application of the coating composition such as by dipping the substrate in a cleaner and / or deoxidizer bath prior to applying the coating composition. The substrate can also be plated prior to applying the coating composition. As used herein, “plating” refers to depositing a metal over a surface of the substrate.Definitions

[0119] For purposes of this detailed description, it is to be understood that the disclosure may assume alternative variations, except where expressly specified to the contrary.

[0120] 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.

[0121] 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.

[0122] As used herein, “including,” “containing” and like terms are understood in the context of this application to be synonymous with “comprising” and are therefore open-ended and do not exclude the presence of additional undescribed or unrecited elements, materials, or ingredients. As used herein, “consisting of’ is understood in the context of this application to exclude the presence of any unspecified element, material, or ingredient. As used herein, “consisting essentially of’ is understood in the context of this application to include the specified elements, materials, or ingredients and those that do not materially affect the basic and novel characteristics of what is being described.

[0123] 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.

[0124] 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.

[0125] As used herein, a “composition” refers to a solution, mixture, or dispersion that can produce a coating on a substrate surface. “Coating” as used herein includes films, layers, and the like.

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

[0127] As used herein, the term “sealant” refers to a coating that can 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.

[0128] As used herein, a “gap filler composition” refers to a composition that forms a gap filler in its cured state.

[0129] As used herein, a “gap filler” refers to a coating that fills a gap between two substrates 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.

[0130] As used herein, an “adhesive composition” refers to a composition that forms an adhesive in its cured state.

[0131] As used herein, an “adhesive” refers to a coating that produces a load-bearing joint.

[0132] As used herein, a “pottant composition” refers to a composition that, when cured, forms a pottant.

[0133] As used herein, a “pottant” refers to an encapsulant.

[0134] As used herein, a “pre-preg” refers to a composition pre-impregnating reinforcement fibers prior to cure.

[0135] As used herein, a “liquid shim composition” refers to a composition that, when cured, forms a liquid shim.

[0136] As used herein, a “liquid shim” refers to a coating that eliminates gaps between substrate surfaces.

[0137] As further defined herein, ambient conditions generally refer to room temperature (e.g., 23°C to 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.

[0138] 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.

[0139] As used herein, “tack free” means a material that is dry to the touch on the surface and that does not leave a residue when touched see AS5127 / ID).

[0140] As used herein, “polymer” refers to oligomers, homopolymers, and copolymers.

[0141] As used herein, the term “monofunctional” means an atom or molecule that is only capable of reacting to form one new bond.

[0142] As used herein, the term “polyfunctional” means an atom or a molecule that is capable of reacting to form more than one new bond more than one time through the same atom and / or through multiple single reactions of atoms within the molecule. For clarity, polyfunctional includes difunctional.

[0143] 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.

[0144] 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.

[0145] As used herein, “alkyl” refers to an aliphatic hydrocarbon group which may be straight or branched and comprising carbon atoms in a chain. Branched means that one or more alkyl groups such as methyl, ethyl or propyl, are attached to a linear alkyl chain. “Alkyl” may be unsubstituted or optionally substituted by one or more substituents which may be the same or different, each substituent being independently selected from the group consisting of halo, alkyl, aryl, cycloalkyl, cyano, hydroxy, alkoxy, alkylthio, amino, — NH(alkyl), — NH(cycloalkyl), — N(alkyl)2, carboxy and — C(O)O-alkyl. Non-limiting examples of suitable alkyl groups include methyl, ethyl, n-propyl, isopropyl and t-butyl.

[0146] 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.

[0147] In view of the foregoing description the present disclosure thus relates to the following Aspects 1 to 119 without being limited thereto.

[0148] Aspect 1. A method of curing a composition, comprising:exposing the composition to electromagnetic radiation (EMR) generated by a laser and / or a light emitting diode (LED) to cure the composition;wherein the composition comprises (a) a thiol-terminated compound and (b) an oxidant.

[0149] Aspect 2. The method of aspect 1, wherein the EMR comprises visible light and / or near infrared light.

[0150] Aspect 3. The method of aspect 1 or aspect 2, wherein the EMR comprises a wavelength of at least 300 nm, such as at least 900 nm.

[0151] Aspect 4. The method of any of the preceding aspects, wherein the EMR comprises a wavelength of at least 960 nm.

[0152] Aspect 5. 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.

[0153] Aspect 6. The method of any of aspects 1 to 4, wherein the EMR comprises a wavelength of no more than 1,080 nm, such as no more than 985 nm.

[0154] Aspect 7. The method of any of aspects 1 to 5, wherein the EMR comprises a wavelength of 300 nm to 2,500 nm, such as 300 nm to 1,500 nm.

[0155] Aspect 8. The method of any of aspects 1 to 3 and 6, wherein the EMR comprises a wavelength of 900 nm to 1,080 nm.

[0156] Aspect 9. The method of any of aspects 1, 2, 4, 6, and 8, wherein the EMR comprises a wavelength of 960 nm to 985 nm.

[0157] Aspect 10. 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.

[0158] Aspect 11. The method of any of the preceding aspects, wherein the EMR is directional.

[0159] Aspect 12. The method of any of the preceding aspects, wherein the EMR comprises monochromatic light and / or polychromatic light.

[0160] Aspect 13. The method of any of the preceding aspects, wherein the EMR is coherent.

[0161] Aspect 14. The method of any of the preceding aspects, wherein the laser is defocused.

[0162] Aspect 15. The method of any of the preceding aspects, wherein the laser generates diffuse EMR, divergent EMR, and / or collimated EMR.

[0163] Aspect 16. 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.

[0164] Aspect 17. 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.

[0165] Aspect 18. 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.

[0166] Aspect 19. The method of any of the preceding aspects, wherein the laser has a wall plug efficiency of at least 80 percent.

[0167] Aspect 20. The method of any of aspects 1 to 19, wherein the laser has a wall plug efficiency of 30 percent to 80 percent, such as 50 percent to 80 percent.

[0168] Aspect 21. The method of any of aspects 1 to 19 and 20, wherein the laser has a wall plug efficiency of 60 percent to 80 percent, such as 30 percent to 50 percent.

[0169] Aspect 22. The method of any of the preceding aspects, wherein the laser and / or the LED comprises adaptive optics such as optics to tailor focal intensity and / or a wide area distribution of the EMR.

[0170] Aspect 23. 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.

[0171] Aspect 24. 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 coating composition, a temperature of a substrate, and / or a ramp rate.

[0172] Aspect 25. The method of any of the preceding aspects, wherein the laser and / or the LED comprises an industrial-sized laser and / or LED.

[0173] Aspect 26. 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.

[0174] Aspect 27. The method of any of the preceding aspects, wherein the oxidant comprises a metal oxide and / or an organic peroxide.

[0175] Aspect 28. The method of any of the preceding aspects, wherein the oxidant comprises activated MnO2.

[0176] Aspect 29. The method of any of the preceding aspects, wherein the composition comprises the oxidant in an amount of at least 0.01 percent by weight based on total weight of the composition, such as at least 0.1 percent by weight.

[0177] Aspect 30. The method of any of the preceding aspects, wherein the composition comprises the oxidant in an amount of at least 0.5 percent by weight based on total weight of the composition.

[0178] Aspect 31. The method of any of the preceding aspects, wherein the composition comprises the oxidant in an amount of no more than 15 percent by weight based on total weight of the composition, such as no more than 10 percent by weight.

[0179] Aspect 32. The method of any of aspects 1 to 31, wherein the composition comprises the oxidant in an amount of 0.01 percent by weight to 15 percent by weight based on total weight of the composition, such as 0.1 percent by weight to 10 percent by weight.

[0180] Aspect 33. The method of any of the preceding aspects, wherein the composition comprises the oxidant in an amount of 0.5 percent by weight to 10 percent by weight based on total weight of the composition.

[0181] Aspect 34. The method of any of the preceding aspects, wherein the thiol-terminated compound comprises a structure of Formula I:HS-R1-SH (I)wherein R1is selected from C2-6 alkanediyl, C6-8cycloalkanediyl, C6-10alkanecycloalkanediyl, C5-8heterocycloalkanediyl, substituted C2-6alkanediyl, substituted C6-8cycloalkanediyl, substituted C6-10alkanecycloalkanediyl, substituted C5-8heterocycloalkanediyl and — [(CHR3)p— X]q— (CHR3)r—; where, each R3is selected from hydrogen and methyl; each X is independently selected from O, S, S — S, NH, and N( — CH3); p is an integer from 2 to 6; q is an integer from 1 to 5; and r is an integer from 2 to 10; wherein each p is independently be 2, 3, 4, 5, and 6, or wherein each p is the same and is 2, 3, 4, 5, or 6.

[0182] Aspect 35. The method of aspect 34, wherein X comprises a heteroatom such as O, S, S-S or another bivalent heteroatom radical; a secondary or tertiary amine group, i.e., — NR6—, where R6is hydrogen or methyl; or another substituted trivalent heteroatom.

[0183] Aspect 36. The method of aspect 34 or aspect 35, wherein X is O or S, and R1is — [(— CH2— )p— O— ]q— (— CH2— )r— or — [(— CH2— )p— S— ]q— (— CH2— )r—, such as wherein p and r are equal, such as wherein p and r each have a value of 2.

[0184] Aspect 37. The method of any of aspects 1 to 33, wherein the thiol-terminated compound comprises a structure of Formula (II):HS— R1— [— S— (CH2)P— O— (— R2— O— )m— (CH2)q— S— R1— ]u— SH (II)wherein R1denotes a C2-10 n-alkylene, C2-6 branched alkylene, C6-8cycloalkylene or C6-10alkylcycloalkylene group, heterocyclic, — [( — CH2)p— X]q— ( — CH2)r; or — [( — CH2)p— X]q— ( — CH2)r— in which at least one — CH2 — unit is substituted with a methyl group; R2denotes a C2-10 n-alkylene, C2-6 branched alkylene, C6-8cycloalkylene or C6-14alkylcycloalkylene group, heterocyclic, — [( — CH2)p— X ]q— ( — CH2)r; X denotes one selected from the group consisting of O, S, S-S and — NR6—; R6denotes H or methyl; m is an independently selected rational numberfrom 1 to 50; and n is an independently selected integer from 1 to 60; 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 from 2 to 10.

[0185] Aspect 38. The method of any of aspects 1 to 33, wherein the thiol-terminated compound comprises formula III:OrB— {R8— S— R1— [— S— CH2CH2— O— (R2— O)m— CH2— S— R1]n— SH}zwherein B denotes a z-valent residue of a polyfunctionalizing agent; R1denotes a C2-10 n-alkylene, C2-6 branched alkylene, C6-8cycloalkylene or C6-10alkylcycloalkylene group, heterocyclic, — [( — CH2)P— X]q— ( — CH2)r; or — [( — CH2)P— X]q— ( — CH2)t— in which at least one — CH2— unit is substituted with a methyl group; R2denotes a C2-10 n-alkylene, C2-6 branched alkylene, C6-8cycloalkylene or C6-14alkylcycloalkylene group, heterocyclic, — [( — CH2)P— X]q— ( — CH2)r; m is an independently selected rational number from 1 to 50; n is an independently selected integer from 1 to 60; R8denotes a residue of a terminal vinyl group or mercapto group; and z is an integer from 3 to 6.

[0186] Aspect 39. The method of aspect 37 or aspect 38, wherein R1is C2-C6 alkyl and R2is C2-C6alkyl.

[0187] Aspect 40. The method of any of the preceding aspects, wherein the thiol-terminated compound has a weight average molecular weight of at least 200 g / mol, such as at least 1,000 g / mol; wherein weight average molecular weight is measured by gel permeation chromatography using polystyrene standards for calibration.

[0188] Aspect 41. The method of any of the preceding aspects, wherein the thiol-terminated compound has a weight average molecular weight of at least 2,000 g / mol; wherein weight average molecular weight is measured by gel permeation chromatography using polystyrene standards for calibration.

[0189] Aspect 42. The method of any of the preceding aspects, wherein the thiol-terminated compound has a weight average molecular weight of no more than 10,000 g / mol, such as no more than 8,000 g / mol; wherein weight average molecular weight is measured by gel permeation chromatography using polystyrene standards for calibration.

[0190] Aspect 43. The method of any of the preceding aspects, wherein the thiol-terminated compound has a weight average molecular weight of no more than 6,000 g / mol; wherein weight average molecular weight is measured by gel permeation chromatography using polystyrene standards for calibration.

[0191] Aspect 44. The method of any of aspects 1 to 42, wherein the thiol-terminated compound has a weight average molecular weight of 200 g / mol to 10,000 g / mol, such as 1,000 g / mol to 8,000 g / mol; wherein weight average molecular weight is measured by gel permeation chromatography using polystyrene standards for calibration.

[0192] Aspect 45. The method of any of aspects 1 to 39, 41, 43, and 44, wherein the thiol-terminated compound has a weight average molecular weight of 2,000 g / mol to 6,000 g / mol; wherein weight average molecular weight is measured by gel permeation chromatography using polystyrene standards for calibration.

[0193] Aspect 46. The method of any of the preceding aspects, comprising the thiol-terminated compound 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.

[0194] Aspect 47. The method of any of the preceding aspects, comprising the thiol-terminated compound in an amount of no more than 99 percent by weight based on total weight of the composition, such as no more than 75 percent by weight.

[0195] Aspect 48. The method of any of the preceding aspects, comprising the thiol-terminated compound in an amount of 20 percent by weight to 99 percent by weight based on total weight of the composition, such as 40 percent by weight to 75 percent by weight.

[0196] Aspect 49. The method of any of the preceding aspects, wherein the composition further comprises a cure retarder and / or a cure accelerator.

[0197] Aspect 50. The method of aspect 49, wherein the cure retarder comprises an acid such as a fatty acid, an organic acid, an inorganic acid, and / or a fatty acid salt; and / or a polysulfide such as phenylphosphonic acid and / or itaconic acid.

[0198] Aspect 51. The method of aspect 49 or aspect 50, wherein the cure accelerator comprises a thiazole, a thiuram, a sulfenamide, a guanidine, a dithiocarbamate, a xanthate, a thiourea, and / or an aldehydeamine.

[0199] Aspect 52. The method of any of aspects 49 to 51, wherein the composition comprises the cure retarder and / or the cure accelerator in an amount of at least 0.01 percent by weight based on total weight of the composition, such as at least 0.1 percent by weight.

[0200] Aspect 53. The method of any of aspects 49 to 52, wherein the composition comprises the cure retarder and / or the cure accelerator in an amount of no more than 7 percent by weight based on total weight of the composition, such as no more than 4 percent by weight.

[0201] Aspect 54. The method of any of aspects 49 to 53, wherein the composition comprises the cure retarder and / or the cure accelerator in an amount of 0.01 percent by weight to 7 percent by weight based on total weight of the composition, such as 0.1 percent by weight to 4 percent by weight.

[0202] Aspect 55. The method of any of the preceding aspects, wherein the composition further comprises an additive(s) and / or a filler.

[0203] Aspect 56. The method of aspect 55, wherein the additive(s) comprises a rheology modifier, a dispersant, a tackifier, a thermoplastic polymer, a surfactant, a flame retardant, a corrosion inhibitor, a UV stabilizer, a colorant, a tint, a solvent, a reactive diluent, a plasticizer, an adhesion promoter, and / or a moisture scavenger.

[0204] Aspect 57. The method of aspect 55 or aspect 56, wherein the composition comprises the additive(s) in a combined amount of at least 0.1 percent by weight based on total weight of the coating composition, such as at least 1 percent by weight.

[0205] Aspect 58. The method of any of aspects 55 to 57, wherein the composition comprises the additive(s) 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.

[0206] Aspect 59. The method of any of aspects 55 to 58, wherein the composition comprises the additive(s) in a combined amount of 0.1 percent by weight to 30 percent by weight based on total weight of the composition, such as 1 percent by weight to 20 percent by weight.

[0207] Aspect 60. The method of any of aspects 55 to 59, wherein the filler comprises aluminum hydroxide, mica, wollastonite, calcium carbonate, glass microspheres, and / or clay.

[0208] Aspect 61. The method of any of the aspects 55 to 60, wherein the composition comprises the filler in an amount of at least 0.1 percent by weight based on total weight of the composition, such as at least 1 percent by weight.

[0209] Aspect 62. The method of any of the aspects 55 to 61, wherein the composition comprises the filler in an 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.

[0210] Aspect 63. The method of any of the aspects 55 to 62, wherein the composition comprises the filler in an amount of 0.1 percent by weight to 30 percent by weight based on total weight of the composition, such as 1 percent by weight to 20 percent by weight.

[0211] Aspect 64. 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.

[0212] Aspect 65. 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 the composition.

[0213] Aspect 66. The method of any of the preceding aspects, 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.

[0214] Aspect 67. The method of any of the preceding aspects, 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.

[0215] Aspect 68. The method of any of aspects 1 to 63, wherein the composition has a total solids content of 100 percent by weight based on total weight of the composition.

[0216] Aspect 69. The method of any of the preceding aspects, wherein the composition is formulated as a liquid.

[0217] Aspect 70. 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.

[0218] Aspect 71. 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, a liquid shim composition, and / or a composition suitable for molding, casting, extrusion, and / or machining.

[0219] Aspect 72. 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.

[0220] Aspect 73. The method of any of the preceding aspects, wherein the composition is exposed to the EMR for at least 20 minutes.

[0221] Aspect 74. 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.

[0222] Aspect 75. 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.

[0223] Aspect 76. 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.

[0224] Aspect 77. The method of any of aspects 1 to 75, wherein the composition is exposed to the EMR at an intensity of no more than 104W / cm2, such as no more than 102W / cm2.

[0225] Aspect 78. The method of any of aspects 1 to 75, 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.

[0226] Aspect 79. The method of any of aspects 1 to 76, 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.

[0227] Aspect 80. The method of any of aspects 1 to 75, 77, 79, 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.

[0228] Aspect 81. The method of any of aspects 1 to 75 and 78, 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.

[0229] Aspect 82. The method of any aspects 72 to 81, comprising cleaning and / or deoxidizing the surface of the substrate.

[0230] Aspect 83. The method of any of aspects 72 to 82, comprising coating the surface of the substrate with a second coating composition in addition to the composition.

[0231] Aspect 84. The method of aspect 83, wherein the second coating composition comprises a pretreatment composition, an electrodepositable coating composition, a primer coating composition, a basecoat coating composition, an adhesion promoter, and / or a topcoat coating composition.

[0232] Aspect 85. The method of any of aspects 72 to 84, comprising applying the composition to a damaged portion of the surface of the substrate.

[0233] Aspect 86. The method of any of aspects 72 to 85, 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.

[0234] Aspect 87. The method of any of aspects 72 to 86, wherein a temperature of the substrate and / or a temperature of the surface of the substrate does not increase upon the exposure to EMR.

[0235] Aspect 88. The method of any of the preceding aspects, further comprising flashing the coating composition prior to the exposing.

[0236] Aspect 89. The method of any of the preceding aspects, further comprising dark curing the composition.

[0237] Aspect 90. The method of aspect 89, wherein the dark curing is for a period of no more than 336 hours, such as no more than 168 hours.

[0238] Aspect 91. The method of aspect 89 or aspect 90, wherein the dark curing is for a period of no more than 96 hours, such as no more than 72 hours.

[0239] Aspect 92. The method of any of aspects 89 to 91, wherein the dark curing is for a period of no more than 24 hours.

[0240] Aspect 93. The method of any of the preceding aspects, wherein a rate of the curing is accelerated compared to a rate of curing the composition under ambient conditions.

[0241] Aspect 94. The method of any of the preceding aspects, wherein a total energy density required to ramp and maintain a temperature of the composition at a temperature setpoint is less than a total energy density required to ramp and maintain a composition that did not include the oxidant at the temperature setpoint.

[0242] Aspect 95. The method of any of the preceding aspects, wherein a total energy density required to ramp and maintain a temperature of the composition at a temperature setpoint is less than 2,000 J / cm2, such as less than 1,500 J / cm2.

[0243] Aspect 96. The method of any of the preceding aspects, wherein a total energy density required to ramp and maintain a temperature of the composition at a temperature setpoint was less than 1,200 J / cm2, such as less than 1,100 J / cm2.

[0244] Aspect 97. The method of any of the preceding aspects, wherein a total energy density required to ramp and maintain a temperature of the composition at a temperature setpoint is reduced by at least 30% compared to a total energy density required to ramp and maintain a composition that did not comprise the oxidant at the temperature setpoint, such as reduced by at least 40%.

[0245] Aspect 98. The method of any of the preceding aspects, wherein a total energy density required to ramp and maintain the coating composition at a temperature setpoint was reduced by at least 50% compared to a total energy density required to maintain a coating composition that did not comprise the oxidant at the temperature setpoint.

[0246] Aspect 99. The method of any of aspects 95 to 98, wherein the temperature setpoint is 110°C.

[0247] Aspect 100. The method of any of aspects 24 to 99, wherein a temperature of the substrate following exposure to the EMR is below a heat deflection temperature of the substrate.

[0248] Aspect 101. The method of any of aspects 72 to 100, further comprising contacting a surface of a second substrate to the composition such that the composition is between the substrate and the second substrate.

[0249] Aspect 102. The method of any of aspects 72 to 101, wherein a temperature of the surface of the substrate does not exceed 121°C upon exposure to EMR.

[0250] Aspect 103. A substrate comprising a coating formed from the coating composition cured by the method of any of the preceding aspects.

[0251] Aspect 104. The substrate of aspect 103, wherein the coating is a sealant, an adhesive, a gap filler, a pottant, a prepreg, a liquid shim, and / or 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.

[0252] Aspect 105. The substrate of aspect 103 or aspect 104, wherein, at least 40 minutes following termination of the exposure to EMR, the coating has a Shore A hardness of at least 25, such as at least 30; wherein the Shore A hardness is measured according to AS5127 / ID.

[0253] Aspect 106. The substrate of any of aspects 103 to 105, wherein, at least 72 to 96 hours following termination of the exposure to EMR, the coating has a Shore A hardness of at least 40, such as at least 45; wherein the Shore A hardness is measured according to AS5127 / 1D.

[0254] Aspect 107. The substrate of any of aspects 103 to 106, wherein, at least 72 to 96 hours following termination of the exposure to EMR, the coating has a Shore A hardness of at least 50; wherein the Shore A hardness is measured according to AS5127 / ID.

[0255] Aspect 108. The substrate of any of aspects 103 to 107, wherein, at least 168 hours following termination of the exposure to EMR, the coating has a Shore A hardness of at least 15, such as at least 20; wherein the Shore A hardness is measured according to AS5127 / ID.

[0256] Aspect 109. The substrate of any of aspects 103 to 108, wherein, at least 168 hours following termination of the exposure to EMR, the coating has a Shore A hardness of at least 25, such as at least 30; wherein the Shore A hardness is measured according to AS5127 / ID.

[0257] Aspect 110. The substrate of any of aspects 103 to 109, wherein, at least 168 hours following termination of the exposure to EMR, the coating has a Shore A hardness of at least 35, such as at least 40; wherein the Shore A hardness is measured according to AS5127 / ID.

[0258] Aspect 111. The substrate of any of aspects 103 to 110, wherein, at least 168 hours following termination of the exposure to EMR, the coating has a Shore A hardness of at least 45, such as at least 50; wherein the Shore A hardness is measured according to AS5127 / ID.

[0259] Aspect 112. The substrate of any of aspects 103 to 111, wherein, at least 336 hours following termination of the exposure to EMR, the coating has a Shore A hardness of at least 20, such as at least 25; wherein the Shore A hardness is measured according to AS5127 / 1D.

[0260] Aspect 113. The substrate of any of aspects 103 to 112, wherein, at least 336 hours following termination of the exposure to EMR, the coating has a Shore A hardness of at least 30, such as at least 35; wherein the Shore A hardness is measured according to AS5127 / 1D.

[0261] Aspect 114. The substrate of any of aspects 103 to 113, wherein, at least 336 hours following termination of the exposure to EMR, the coating has a Shore A hardness of at least 40, such as at least 45; wherein the Shore A hardness is measured according to AS5127 / ID.

[0262] Aspect 115. The substrate of any of aspects 103 to 114, wherein, at least 336 hours following termination of the exposure to EMR, the coating has a Shore A hardness of at least 50, such as at least 55; wherein the Shore A hardness is measured according to AS5127 / 1D.

[0263] Aspect 116. The substrate of any of aspects 103 to 115, wherein the surface of the substrate is tack-free at least 40 minutes following termination of the exposure to EMR.

[0264] Aspect 117. A coating application kit for a 2K composition, the kit comprising: (a) a cartridge assembly comprising:(i) a cartridge comprising a first component of the 2K composition; and(ii) an injector containing a second component of the 2K composition; wherein the cartridge and the injector are structured and arranged to allow the second component to flow into the cartridge to form a coating composition; and(b) instructions for exposing the coating composition to defocused electromagnetic radiation (EMR) generated by a laser to cure the coating composition.

[0265] Aspect 118. A coating application kit for a 2K composition, the kit comprising: (a) a cartridge assembly comprising:(i) a cartridge comprising a first compartment containing a first component of the 2K composition, a second compartment containing a second component of the 2K composition, and a barrier separating the first compartment and the second compartment; and(ii) a piercer structured and arranged to break the barrier to allow the first component and the second component to flow together to form a coating composition; and(b) instructions for exposing the coating composition to defocused electromagnetic radiation (EMR) generated by a laser to cure the coating composition.

[0266] Aspect 119. The kit of aspect 117 or aspect 118, wherein the instructions comprise instructions to perform the method of any of aspects 1 to 102.

[0267] Illustrating the disclosure are the following examples, which, however, are not to be considered as limiting the disclosure to their details.EXAMPLES

[0268] The compositions were prepared and mixed using a Hauschild Speedmix DAC mixer, model 600.1 FVZ. The formulations comprised two parts (Part A and Pail B). Pail A was prepared by combining all the listed components in Table I, in listed order. The materials were mixed prior to the filler addition and after all components were added on the DAC mixer for 45 seconds at 1800 rpm. The mixture was inspected and mixed manually with a spatula toensure homogeneity. Part B was prepared in the same manner as Part A, combining all the listed components in listed order in Table 1.Table 1. Compositions 1 to 51accelerator, dipentamethylene thiuramhexasulfide supplied by Vanderbilt Chemicals2thiol-terminated compound (Mw of 3,400 g / mol to 3,600 g / mol) supplied by Nouryon3thiol-terminated compound (Mw of 3,900 g / mol to 4,400 g / mol) supplied by Nouryon4adhesion promoter, allyl ether phenolic polymer supplied by Sumitomo Bakelite North America, Inc.Test Sample Preparation

[0269] Parts A and B were mixed in the ratios listed in Table 1, then subsequently drawn down at a 1 / 8” thickness, using 1 / 8” shims, for all testing. Shore A hardness samples weredrawn down on Teflon substrates. Cure (reported as Shore A hardness measured according to SAE AS5127 / ID, which references ASTM D2240-15) of the samples was monitored at the time points reported for a period of 14 days (336 hours) with a final Shore A hardness reported in Tables 2 to 4. As used herein, “final Shore A hardness” refers to the Shore A hardness recorded at the final time tested.

[0270] 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 Teflon substrates.Compositions were exposed to the EMR with a 30 second ramp from ambient to a temperature setpoint of 110°C and then held at 110°C for 20 minutes. Shore A hardness was measured after the coating cooled to ambient temperature. Shore A hardness of Compositions 2 to 4 was measured as described above at the time points reported over a period of 14 days (336 hours). Data are reported in Table 2 and shown graphically in FIGS. 1 to 3.

[0271] Oven-exposed samples. Samples were drawn down on Teflon substrates and cured in an oven at 110°C for 20 minutes, then Shore A hardness was measured after the coating composition cooled to ambient temperature. Shore A hardness was measured as described above at the time points reported over a period of 14 days (336 hours). Data are reported in Table 3 and shown graphically in FIGS. 1 to 3.

[0272] Ambient-cured samples. Samples were drawn down on Teflon substrates and placed in an environment-controlled cabinet (Forma #3940) at 25°C, 50% relative humidity. Shore A harness was measured as described above at least 20 minutes following draw down and then at the time points reported over a period of 14 days (336 hours). Data are reported in Table 4 and shown graphically in FIGS. 1 to 3.

[0273] Total Energy Density calculation. Total Energy Density was calculated according to Equation 1:Zmax%P x LpAX AtfoEquation 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 tmax includes ramp time to a temperature setpoint and hold time at the temperature setpoint (in seconds); %P = the percentage of laser power used in the recorded time interval (as recorded using LASCON Process Manager software by Dr. Mergenthaler GmbH & Co. KG, as pail of the controller of the laser system; Lp - laser power, 4500 W; At = 0.02 seconds between recorded data points,; and = the projection area of the laser output, 20 cm x 20 cm = 400 cm2. As used herein, “temperature setpoint” refers to a preset temperature to which the coating is ramped and at which the coating is maintained over the heating cycle. Temperature setpoint may be measured using an infrared thermometer or similar device to measure the temperature of the coating. Temperatures from the infrared thermometer may be read by the controller described above to adjust the EMR generated by the laser system over the heating cycle to ramp or maintain the coating temperature at the temperature setpoint.

[0274] Total Energy Density data are reported in Table 6.Table 2: Shore A Hardness Cure Profile Post-Laser ExposureTable 3: Shore A Hardness Cure Profile Post-Oven Exposure* Denotes sample was tackyTable 4: Shore A Hardness Cure Profile Under Ambient ConditionsTable 5: Final Shore A Hardness Values Showing Mechanical Performance** Shore A Hardness at 14 days. Data are copied from Table 2 above.*** Shore A Hardness at 14 days. Data are copied from Table 3 above.**** Shore A Hardness at 14 days. Data are copied from Table 4 above.Table 6: Total Energy Density Data

[0275] Compositions comprising a thiol-terminated compound and an oxidant were exposed to laser, oven, or ambient cure conditions as described above. The cure profiles were monitored over 336 hours using Shore A hairiness measurements.

[0276] The data in Tables 2 to 4 show the cure profiles (Shore A hardness) of Examples 1 to 5 under different cure conditions (i.e., post-laser exposure, post-oven exposure, and ambient, respectively). Data are reported graphically in FIG. 1 to 3.

[0277] As expected, Examples 1 and 5, which did not include an oxidant (c.g., activated MnCE), did not cure under any conditions.

[0278] Examples 2-4 each developed hardness over time, regardless of cure conditions. However, cure was dependent on the amount of oxidant present as shown in comparison of Shore A hardness of Example 2 with Examples 3 and 4. Example 2 partially cured but did not reach the same final hardness (Shore A hardness > 49) as Examples 3 and 4.

[0279] Both laser- and ambient-cured Examples reached similar final Shore A hardness at 336 hours, as shown in Table 5. These data demonstrate that curing continued even after the initial exposure to laser, oven, or ambient conditions. As shown in Example 4, thermal stimuli (i.e., oven) negatively impacted Shore A hardness unless high enough accelerator levels were used.

[0280] As shown in Table 2, laser-exposed samples cured faster than oven-exposed samples, as demonstrated by Shore A hardness values measured at Day 0 for laser-exposed samples. Dark cure continued in the days following laser exposure as demonstrated by the continued increase in Shore A hardness at 72-96 hours, 168 hours, and 336 hours. In contrast, as shown in Table 3, oven-exposed samples did not show an increase in Shore A hardness until after Day 0. Additionally, oven-exposed samples reached a lower final Shore A hardnesscompared to laser-exposed and ambient-cured samples, indicating that oven-exposure negatively impacted dark cure. These results unexpectedly demonstrated that curing samples using the laser may be advantageous, such as to achieve mechanically robust coatings shortly after application of the composition to the substrate, while maintaining dark cure to achieve a final Shore A hardness similar to that observed with ambient-cured samples.

[0281] Total energy density data are reported in Table 6. Example 1, which did not include an oxidant, required the highest total energy density to maintain a temperature of 110°C. Examples 2-5, which all included MnCE, required less total energy density to maintain a temperature of 110°C compared to Example 1.

[0282] Whereas specific aspects of the disclosure have been described in detail, it will be appreciated by those skilled in the art that various modifications and alternatives to those details could be developed in light of the overall teachings of the disclosure. Accordingly, the particular arrangements disclosed are meant to be illustrative only and not limiting as to the scope of the disclosure which is to be given the full breadth of the claims appended and any and all equivalents thereof.

Claims

1. We claim:

1. A method of curing a coating composition, comprising:3.exposing the coating composition to electromagnetic radiation (EMR) generated by a defocused laser to cure the coating composition;4.wherein the coating composition comprises (a) a thiol-teiminated compound and (b) an oxidant.

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 coating composition is exposed to the EMR for at least 10 minutes.

7. The method of any of the preceding claims, wherein the coating composition comprises the oxidant in an amount of 0.1 percent by weight to 20 percent by weight based on total weight of the coating composition.

8. The method of any of the preceding claims, wherein the oxidant comprises an activated MnO2.

9. The method of any of the preceding claims, wherein the coating composition is a liquid.

10. The method of any of the preceding claims, wherein the coating composition is formulated as a two-component composition and / or as a PMF.

11. The method of any of the preceding claims, wherein a tack-free surface of the coating composition is achieved at least 90 minutes following termination of the exposure to the EMR.

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

13. The method of claim 12, wherein the dark-curing is for a period of up to 14 days.

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

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

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

17. The substrate of claim 16, wherein the cured coating composition has:20.(a) a Shore A hairiness, at least 40 minutes following termination of the exposure to the EMR, of at least 20;21.(b) a Shore A hardness of at least 40 at least 96 hours following termination of the exposure to the EMR;22.(c) a Shore A hardness of at least 25 at least 168 hours following termination of the exposure to the EMR; and / or23.(d) a final Shore A hairiness of at least 20 at least 336 hours following termination of the exposure to the EMR; wherein the Shore A hardness is measured according to AS5127 / ID.

18. A coating application kit for a 2K composition, the kit comprising:24.(a) a cartridge assembly comprising:25.(i) a cartridge comprising a first component of the 2K composition; and26.(ii) an injector comprising a second component of the 2K composition; wherein the cartridge and the injector are structured and arranged to allow the second component to flow into the cartridge to form a composition; and27.(b) instructions for exposing the coating composition to electromagnetic radiation (EMR) generated by a laser to cure the composition.

19. A coating application kit for a 2K composition, the kit comprising:29.(a) a cartridge assembly comprising:30.(i) a cartridge comprising a first compartment containing a first component of 2K the composition, a second compartment containing a second component of the 2K composition, and a barrier separating the first compartment and the second compartment; and31.(ii) a piercer structured and arranged to break the barrier to allow the first component and the second component to flow together to form a composition; and32.(b) instructions for exposing the coating composition to electromagnetic radiation (EMR) generated by a laser to cure the coating composition.

20. The coating application kit of claiml8 or claim 19, wherein the instructions comprise instructions to perform the method of any of claims 1 to 15.

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