[0002] Various coatings are commonly utilized in automotive paint operations, including primers, base coats and clear coats. However, many of these coatings require strict environmental and processing considerations in order to prevent undesirable imperfections on the painted surface.

[0003] United States Patent Nos. 8,652,578; 8,653,183 7,399,393; and 7,183,000 may be relevant to the present teachings and are all incorporated by reference for all purposes.

[0004] Notwithstanding the above teachings, there remains a need for a coating material and process that minimizes the need for certain environmental and processing requirements. Summary of the Invention

[0005] One or more of the above needs are met by the present teachings which contemplate a method comprising locating an uncured coating composition onto a substrate, the coating composition including an activating agent, forming a permeable skin on the coating composition via activation of the activating agent, the permeable skin forming in less than 1 minute. The skin is substantially free of any tack and the uncured coating is adapted to cure and evaporate solvents through the permeable skin. The permeable skin substantially prevents airborne or other contaminants from embedding in the uncured coating.

[0006] The activating agent may be encapsulated. The coating composition may comprise a clearcoat material. The method may include activating the activating agent by ultraviolet light, heat, infrared light, convection, induction, humidity, moisture, or some combination thereof. The method may include reacting the activating agent with one or more components of the coating composition to form the permeable skin. The method may include releasing the encapsulated activating agent during contact with a rotary paint atomizer or the like. The method may include forming the permeable skin in less than two minutes. The method may include forming the permeable skin in less than 30 seconds. [0007] The teachings herein are further directed to a coating composition comprising one or more pigments, one or more solvents or diluents; and at least one activating agent for forming a permeable skin layer due to one or more of: the shearing effect of a rotary atomizer; reaction of the at least one activating agent with one or more additional components; exposure to a stimulus; contact with a substrate; contact with a second composition or any combination thereof.

[0008] The composition may include one or more solvents. The composition may include an ethylene-based component. The composition may include a polytetrafluoroethylene component. The composition may include an acrylic component. The composition may include a styrenic component. The composition may include one or more pigments, solvents, diluents, binders, UV stabilizers, or any combination thereof. The composition may include a terpolymer component. The composition may include one or more thermoset components. The composition may include one or more thermoplastic components. The composition may include a silicone component. The composition may include a fluorocarbon component. The composition may include a polyethylene component.

[0009] The teachings herein are directed generally to coating compositions and methods of applying coating compositions so that a permeable skin is quickly formed by the coating. Detailed Description

[00010] The explanations and illustrations presented herein are intended to acquaint others skilled in the art with the invention, its principles, and its practical application. The specific embodiments of the present invention as set forth are not intended as being exhaustive or limiting of the invention. The scope of the invention should be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. The disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. Other combinations are also possible as will be gleaned from the following claims, which are also hereby incorporated by reference into this written description.

[00011] This application claims the benefit of the filing date of United States Provisional Application Serial No.62/852,634, filed on May 24, 2019, the contents of that application being hereby incorporated by reference for all purposes.

[00012] The coatings described herein include a component that can be activated prior to, during, substantially during, or after application of the coating to a substrate. The substrate may be a metallic substrate, such as those utilized for forming vehicle panels, but may alternatively be a polymeric material, or a composite material including some combination of metallic materials and polymeric materials, any of which may be in the form of sheets, fibers, pastes, films, or any other formats commonly utilized in forming composites.

[00013] The coating may be activated by a physical or chemical activating agent. For example, an activating agent within the coating may be physically contacted prior to or during application of the coating such that the physical contact causes activation of the agent. Alternatively, the activating agent may be reacted with a secondary material, or a component already within the coating that may cause activation of the activating agent. In either of these scenarios, it is possible that the activating agent may be encapsulated. Thus, any physical initiation could cause failure of the encapsulation and exposure of the activating agent, or a chemical reaction could cause the desired failure of encapsulation. It is also possible that the coating be formulated as a two-part material, where the activating agent is located in a first part of the coating material and a component for reacting with the activating agent is located in a second part of the coating material.

[00014] The activating agent may be activated to form a skin on the surface of a substrate. The skin is formulated to allow solvents to evaporate through the skin, while maintaining a tack-free surface so that dust and other undesirable particulates do not adhere to the coated substrate.

[00015] The activating agent may be activated by a shearing effect as the coating travels through a paint atomizer. The activating agent may be activated by ultraviolet light, heat, infrared light, convection, induction, humidity, moisture, or some combination thereof. The activating agent may act as a curing agent that activates upon contact with one or more additional components of the coating. It is possible that such activation causes polymerization of the coating. It is also possible that the coating is applied to a substrate that includes a material (either inherently or by addition of a chemical composition) that causes activation of the activating agent.

[00016] In the event that the activating agent is encapsulated, the activating agents may include a shell containing the activating agent within the shell. As used herein the term shell means a small structure of any shape and texture containing a core or internal space that is enclosed within the structure. It is also possible that activating agent is included within (or partially within) a solid matrix type material. Examples of such arrangements are disclosed in U.S. Patent Publication No.2015/0132592. [00017] The encapsulating material will protect or isolate the activating agent from initiating a reaction with the remainder of the components within the coating and will upon exposure to or application of physical or chemical modification release some or all of the activating agent. The encapsulation material may comprise a polymeric material which may be a crosslinked polymeric material. The encapsulating material may be made of gelatin, polyoxymethylene urea formaldehyde, melamine formaldehyde, polyurethane, silica, some combination thereof or the like.

[00018] The activating agent may have a crosslinking capability. The crosslinking capability may be provided by aliphatic or aromatic amines or their respective adducts, amidoamines, polyamides, cycloaliphatic amines, anhydrides, polycarboxylic polyesters, isocyanates, phenol-based resins (e.g., phenol or cresol novolac resins, copolymers such as those of phenol terpene, polyvinyl phenol, or bisphenol-A formaldehyde copolymers, bishydroxyphenyl alkanes or the like), dihydrazides, sulfonamides, diamino diphenyl sulfone, anhydrides, mercaptans, imidazoles, ureas, tertiary amines, boron trifluoride complexes, or any combination thereof. The activating agent(s) may be selected from modified and unmodified polyamines or polyamides, triethylenetetramine, diethylenetriamine, tetraethylenepentamine, cyanoguanidine, dicyandiamides, or any combination thereof. The activating agent may be based on an acid. The activating agent may be a salt or ester of an acid. The activating agent may be based upon a carboxylic acid. The activating agent may include one or more of carbonic acid, formic acid, methanoic acid, benzoic acid, acetic acid, propionic acid, caproic acid, or the salt or ester of these acids. The activating agent may be dibutyltin dilaurate. The activating agent may be utilized to accelerate the reaction time. The activating agent may be useful to control the activation rate. The activation could be accelerated by heat application in some cases, but it is not essential.

[00019] It is possible that the coating itself may be free of any activating agent, but rather an activating agent is applied to the substrate which will receive the coating. Alternatively, the coating may be applied to a substrate that is free of any activating agent. The substrate to which the coating is applied may be a reactive substrate. The substrate to which the coating is applied may be a nonreactive substrate.

[00020] Acrylic or acrylic hybrid polymers may be utilized to form the coating. The coating may include polyurethane materials. These materials may be formulated with polymerization and cross-linking schemes commensurate with typical acrylate or urethane chemistries. The coating may also include low-odor and/or non-flammable (e.g. flame resistant) polymeric materials. Various polymeric materials may be included in the coating, such as thermoplastic materials including polyethylene and polyurethane, and the like. Additional materials may also be included in the coating including but not limited to antioxidants, stabilizers, solvents, initiators and crosslinkers.

[00021] The coating may include one or more acrylate monomers, which may be methacrylate monomers. The coating may include at least 10% acrylate monomers, at least 20% acrylate monomers, at least 40% acrylate monomers, or even at least 60% acrylate monomers by weight of the total coating composition. The coating may include less than 80% acrylate monomers, less than 60% acrylate monomers, or even less than 40% acrylate monomers.

[00022] The coating may include one or more elastomeric materials. The elastomeric materials may be present in an amount of at least 5%, at least 10%, at least 20% or even at least 30% by weight of the coating composition. The elastomers may be present in an amount of less than 50%, less than 40%, less than 30% or even less than 20% by weight of the coating composition. The one or more elastomers may be one or any combination of chlorosulfonated polyethylene, chlorinated polyethylene, carboxy-terminated butadiene-acrylonitrile copolymers, vinyl-terminated butadiene-acrylonitrile copolymers, styrene-butadiene-styrene copolymers, polychloroprene, or acrylonitrile-butadiene rubber.

[00023] The coating may include one or more polymeric polyols. Such polymeric polyols may include (meth)acrylic polyols, polyester polyols, polyurethane polyols, polyether polyols, and combinations thereof. The polymeric polyols may have a hydroxyl equivalent weight ranging from 100 to 1000 grams per equivalent, or even 150 to 500 grams per equivalent. The polymeric polyols may also have a glass transition temperature of less than 60° C, less than 40° C, or even less than 22° C. Such polymeric polyols may include carboxyl groups that can be prepared from polymerizable ethylenically unsaturated monomers, such as copolymers of (meth)acrylic acid and hydroxylalkyl esters of (meth)acrylic acid with one or more other polymerizable ethylenically unsaturated monomers such as alkyl esters of (meth)acrylic acid including methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethyl hexylacrylate, and vinyl aromatic compounds, such as styrene, alpha-methyl styrene and vinyl toluene.

[00024] The coating may include polymeric polyols with epoxy functional groups. Such polyols may be prepared from polymerizable ethylenically unsaturated monomers by copolymerizing oxirane group-containing monomers, for example glycidyl (meth)acrylate and allyl glycidyl ether, with other polymerizable ethylenically unsaturated monomers. The coating may include polymeric polyols with carbamate functional groups. These polyols may be prepared from polymerizable ethylenically unsaturated monomers by copolymerizing ethylenically unsaturated monomers with a carbamate functional vinyl monomer such as a carbamate functional alkyl ester of methacrylic acid. Carbamate functional groups can also be incorporated into the polymeric polyol by reacting the polymeric polyol with a low molecular weight alkyl carbamate such as methyl carbamate. Preferred polymeric polyols may be polyester polyols. Examples of polyester polyols include the condensation products of polyhydric alcohols and polycarboxylic acids. The polyhydric alcohols may include ethylene glycol, neopentyl glycol, trimethylolpropane, and pentaerythritol. The polycarboxylic acids may include adipic acid, 1,4-cyclohexyl dicarboxylic acid, and hexahydrophthalic acid. In addition to the polycarboxylic acids mentioned above, anhydrides can be used. Other suitable polymeric polyols may be polyurethane polyols. The polyurethane polymers may be formed by reacting a polyester polyol with a polyisocyanate to form a polyurethane polymer having hydroxyl functionality. Examples of suitable polyisocyanates include aromatic isocyanates, such as 4,4- diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, and toluene diisocyanate, and aliphatic polyisocyanates, such as 1,4-tetramethylene diisocyanate and 1,6-hexamethylene diisocyanate. Cycloaliphatic diisocyanate, such as 1,4-cyclohexyl diisocyanate and isophorone diisocyanate, also can be utilized.

[00025] The polymeric polyols may be present in an amount of 1% by weight or more of the coating. The polymeric polyols may be present in an amount of 10% by weight or more of the coating. The polymeric polyols may be present in an amount of 20% by weight or more of the coating. The polymeric polyols may be present in an amount of 50% by weight or less of the coating. The polymeric polyols may be present in an amount of 20% by weight or less of the coating. The polymeric polyols may be present in an amount of 5% by weight or less of the coating.

[00026] The coating may include one or more monomers. The monomers may be selected from acrylate, acrylic acid, ethyl acrylate, methacrylate, ethyl cyanoacrylate, ethylene, ethylene oxide, acrylonitrile, 1,3-butadiene, butyl acrylate, butyl cyanoacrylate, cyclobutene, dicyclopentadiene, 3,4-dimethoxystyrene, glycidyl methacrylate, styrene, (hydroxyethyl)methacrylate, N-(2-Hydroxypropyl) methacrylamide, methacrylamide, methacrylic acid, methacrylonitrile, methyl 2-chloroacrylate, methyl 2-fluoroacrylate, methyl acrylate, methyl cyanoacrylate, methyl isocyanate, methyl methacrylate, 1,8-octanediol, octene, octyl cyanoacrylate, 2-octyl cyanoacrylate, trimethylene carbonate, phenylenediamine, tetrafluoroethylene, vinyl acetate, vinyl chloride, vinyl ether, or any combination thereof.

[00027] The coatings may include one or more monomers, such as those described above. Specifically, in utilizing monomers such as malonates and cyanoacrylates, it is possible that many chemical components typically utilized to formulate coatings make the coating unstable. Thus, the coating may comprise only a malonate, a cyanoacrylate, or some combination thereof. However, it is also possible that a number of materials may improve the physical characteristics of the coating without compromising the activation capability of the coating. As such, the coating may be formulated to include one or more additional monomers, one or more polymers, one or more fillers, organic co-solvents, abrasion resistant particles, reactive diluents, catalysts, and other customary components.

[00028] The one or more monomers may be present in an amount of 1% by weight or more of the coating. The one or more monomers may be present in an amount of 10% by weight or more of the coating. The one or more monomers may be present in an amount of 20% by weight or more of the coating. The one or more monomers may be present in an amount of 30% by weight or more of the coating. The one or more monomers may be present in an amount of 40% by weight or more of the coating. The one or more monomers may be present in an amount of 70% by weight or less of the coating. The one or more monomers may be present in an amount of 60% by weight or less of the coating. The one or more monomers may be present in an amount of 50% by weight or less of the coating. The one or more monomers may be present in an amount of 30% by weight or less of the coating. The one or more monomers may be present in an amount of 20% by weight or less of the coating.

[00029] The coatings described herein may further comprise colorants. The colorant can be added to the coating in any suitable form, such as discrete particles, dispersions, solutions and/or flakes. A single colorant or a mixture of two or more colorants can be used in the coatings described herein. In general, the colorant can be present in any amount sufficient to impart the desired visual and/or color effect. Example colorants include pigments, dyes and tints. Example pigments and/or pigment compositions include, but are not limited to, carbazole dioxazine crude pigment, azo, monoazo, disazo, naphthol AS, salt type (lakes), benzimidazolone, condensation, metal complex, isoindolinone, isoindoline and polycyclic phthalocyanine, quinacridone, perylene, perinone, diketopyrrolo pyrrole, thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone, dioxazine, triarylcarbonium, quinophthalone pigments, diketo pyrrolo pyrrole red (“DPPBO red”), titanium dioxide, carbon black, or mixtures thereof. Example dyes include, but are not limited to, phthalo green or blue, iron oxide, bismuth vanadate, anthraquinone, perylene, aluminum and quinacridone. The colorant may be present in an amount of 0.30% by weight or more of the coating. The colorant may be present in an amount of 10% by weight or less of the coating.

[00030] The coatings described herein may include a solvent. Any suitable solvents can be used. Examples include but are not limited to aliphatic or aromatic hydrocarbon such as SOLVESSO 100 solvent or OXSOL 100 solvent, toluene or xylene, an alcohol such as n- butanol, sec-butanol, or isopropanol, an ester such as methyl acetate, n-propyl acetate, iso- butyl acetate, n-butyl acetate, ethyl acetate, ethyl propionate, n-butyl propionate, or n-pentyl propionate, a ketone such as acetone, methyl isobutyl ketone, methyl ethyl ketone, methyl amyl ketone, methyl isoamyl ketone, or methyl n-propyl ketone, an ether, an ether-alcohol or an ether-ester such as ethyl 3-ethoxypropionate, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol n-propyl ether or propylene glycol t-butyl ether, propylene glycol methyl ether acetate or a mixture of any of these. The solvent may be present in an amount of 0.30% by weight or more of the coating. The solvent may be present in an amount of 10% by weight or less of the coating.

[00031] The coatings of the present teachings may also include one or more fillers, including but not limited to particulate materials (e.g., powder), beads, microspheres, or the like. Examples of fillers that may be used include silica, glass, talc, pigments, colorants, glass beads or bubbles. Examples of suitable fillers also include, without limitation, wollastonite, talc, vermiculite, pyrophyllite, sauconite, saponite, nontronite, montmorillonite or mixtures thereof. Silicate minerals such as mica may be used as fillers.

[00032] When employed, the amount of fillers in the coating can range from 2% to more than 30% or greater by weight, but more typical from about 8 to 25% by weight. According to some embodiments, the coating may include from about 0% to about 3% by weight, and more preferably slightly less than 1% by weight silica or similar fillers. Powdered (e.g. about 0.01 to about 50, and more preferably about 1 to 25 micron mean particle diameter) mineral type filler can comprise between about 5% and 40% by weight, more preferably about 10% to about 25% by weight.

[00033] Several additional polymers may be incorporated into the coating. For example, without limitation, other polymers that might be appropriately incorporated into the coating material include halogenated polymers, polycarbonates, polyketones, urethanes, polyesters, silanes, sulfones, allyls, olefins, styrenes, acetates, ethylene vinyl acetates, acrylates, methacrylates, epoxies, silicones, phenolics, rubbers, polyphenylene oxides, terphthalates, or mixtures thereof. Other potential polymeric materials may be or may include, without limitation, polyethylene, polypropylene, polystyrene, polyolefin, polyacrylate, poly(ethylene oxide), poly(ethyleneimine), polyester, polyurethane, polysiloxane, polyether, polyphosphazine, polyamide, polyimide, polyisobutylene, polyacrylonitrile, poly(vinyl chloride), poly(methylmethacrylate), poly(vinyl acetate), poly(vinylidene chloride), polytetrafluoroethylene, polyisoprene, polyacrylamide, polyacrylic acid, polymethacrylate, and polyacetals.

[00034] It is possible that the coating may include one or more additional polymers (e.g., copolymers), which are typically, but not necessarily copolymers or terpolymers. For example, and without limitation, polymers that might be appropriately incorporated into the coating include halogenated polymers, polycarbonates, polyketones, and polymers of urethanes, polyesters, silanes, sulfones, allyls, olefins, styrenes, acrylates, methacrylates, epoxies, silicones, phenolics, rubbers, polyphenylene oxides, terphthalates, acetates (e.g., EVA), acrylates, methacrylates (e.g., ethylene methyl acrylate polymer) or mixtures thereof. Other potential polymeric materials may be or may include, without limitation, polyolefin (e.g., polyethylene, polypropylene) polystyrene, polyacrylate, polyethylene oxide), poly(ethyleneimine), polyester, polyurethane, polysiloxane, polyether, polyphosphazine, polyamide, polyimide, polyisobutylene, polyacrylonitrile, polyvinyl chloride), poly(methyl methacrylate), polyvinyl acetate), poly(vinylidene chloride), polytetrafluoroethylene, polyisoprene, polyacrylamide, polyacrylic acid, polymethacrylate. Although not required, it may be desired for the coating to include one or more ethylene polymers or copolymers such as ethylene acrylates, ethylene acetates, or the like. Ethylene methacrylate and ethylene vinyl acetate are two preferred ethylene copolymers. When used, the one or more additional polymers comprises about 0.1% to about 50%, more preferably about 1% to about 20% and even more preferably about 5% to about 15% by weight of the coating.

[00035] As used herein, unless otherwise stated, the teachings envision that any member of a genus (list) may be excluded from the genus; and/or any member of a Markush grouping may be excluded from the grouping.

[00036] Unless otherwise stated, any numerical values recited herein include all values from the lower value to the upper value in increments of one unit provided that there is a separation of at least 2 units between any lower value and any higher value. As an example, if it is stated that the amount of a component, a property, or a value of a process variable such as, for example, temperature, pressure, time and the like is, for example, from 1 to 90, preferably from 20 to 80, more preferably from 30 to 70, it is intended that intermediate range values such as (for example, 15 to 85, 22 to 68, 43 to 51, 30 to 32 etc.) are within the teachings of this specification. Likewise, individual intermediate values are also within the present teachings. For values which are less than one, one unit is considered to be 0.0001, 0.001, 0.01, or 0.1 as appropriate. These are only examples of what is specifically intended and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application in a similar manner. As can be seen, the teaching of amounts expressed as "parts by weight" herein also contemplates the same ranges expressed in terms of percent by weight. Thus, an expression in the of a range in terms of“at least‘x’ parts by weight of the resulting composition" also contemplates a teaching of ranges of same recited amount of "x" in percent by weight of the resulting composition."

[00037] Unless otherwise stated, all ranges include both endpoints and all numbers between the endpoints. The use of "about" or "approximately" in connection with a range applies to both ends of the range. Thus, "about 20 to 30" is intended to cover "about 20 to about 30", inclusive of at least the specified endpoints.

[00038] The disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. The term "consisting essentially of to describe a combination shall include the elements, ingredients, components or steps identified, and such other elements ingredients, components or steps that do not materially affect the basic and novel characteristics of the combination. The use of the terms "comprising" or "including" to describe combinations of elements, ingredients, components or steps herein also contemplates embodiments that consist of, or consist essentially of the elements, ingredients, components or steps.

[00039] Plural elements, ingredients, components or steps can be provided by a single integrated element, ingredient, component or step. Alternatively, a single integrated element, ingredient, component or step might be divided into separate plural elements, ingredients, components or steps. The disclosure of "a" or "one" to describe an element, ingredient, component or step is not intended to foreclose additional elements, ingredients, components or steps.

[00040] It is understood that the above description is intended to be illustrative and not restrictive. Many embodiments as well as many applications besides the examples provided will be apparent to those of skill in the art upon reading the above description. The scope of the invention should, therefore, be determined not with reference to the above description, but should instead be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. The disclosures of all articles and references, including patent applications and publications, are incorporated by reference for all purposes. The omission in the following claims of any aspect of subject matter that is disclosed herein is not a disclaimer of such subject matter, nor should it be regarded that the inventors did not consider such subject matter to be part of the disclosed inventive subject matter.