# US 11,078,376 B2 · Polyurethane coating compositions containing 1,1-di-activated vinyl compounds and related coatings and processes > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,078,376 B2 - Document ID: US11078376B2 - Status: Granted - Kind: B2 - Application number: 16/320,604 - Filed: 2017-07-26 - Published: 2019-05-30 - Granted: 2021-08-03 - Earliest claimed: 2016-07-26 - Assignees: PPG Industries Ohio, Inc. - Applicants: PPG Industries Ohio, Inc. - Inventors: Aditya Gottumukkala; Scott W. Sisco; David R. Fenn; Daniel F. Moyano; Kurt G. Olson; Matthew S. Luchansky; Richard J. Sadvary; Shiryn Tyebjee; Caroline S. Harris; Shanti Swarup - Web page: https://patentgrep.com/patent/US11078376B2 ## CPC - C09D 175/04: Polyurethanes - B05D 7/572: {all layers being cured or baked together} - B05D 7/574: {at least some layers being let to dry at least partially before applying the next layer (B05D7/577 takes precedence)} - C08G 18/4018: {Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48} - C08G 18/4854: {Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group} - C08G 18/6692: {with compounds of group C08G18/34} - C08G 18/755: {and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate} - C08G 18/792: {formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates} - C08G 18/797: {containing carbodiimide and/or uretone-imine groups} - C08G 71/04: Polyurethanes - C09D 7/63: organic - C09D 133/00: Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers - C09D 133/10: Homopolymers or copolymers of methacrylic acid esters - B05D 3/0254: {After-treatment} - B05D 7/534: {the first layer being let to dry at least partially before applying the second layer (B05D7/538 takes precedence)} - B05D 7/542: {the two layers being cured or baked together} - B05D 2202/10: based on Fe - B05D 2401/20: Aqueous dispersion or solution - B05D 2503/00: Polyurethanes - B05D 2508/00: Polyesters - C08K 5/0025: {Crosslinking or vulcanising agents; including accelerators} - C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D) - B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02) - C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS - C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09) ## Abstract Polyisocyanate-cured coating compositions containing 1,1-di-activated vinyl compounds are described. Also provided are coatings formed from coating compositions comprising 1,1-di-activated vinyl compounds, including multi-layer coatings. Also provided are processes for coating substrates with coating compositions comprising 1,1-di-activated vinyl compounds. Also provided are articles employing the coatings described herein. ## Claims ### Claim 1 A coating composition comprising: (A) a polyfunctional resin; and (B) a crosslinker composition comprising: (b1) a polyisocyanate compound; and (b2) a 1,1-di-activated vinyl compound, or a multifunctional form thereof, or a combination thereof, wherein the 1,1-di-activated vinyl compound comprises a methylene dicarbonyl compound, a dihaloalkyl disubstituted vinyl compound, a multifunctional form of a methylene dicarbonyl compound, a multifunctional form of a dihaloalkyl compound, a multifunctional form of a dihaloalkyl disubstituted vinyl compound, or combination thereof; wherein a mixture of components (A) and (B) form a coating composition. ### Claim 2 (depends on 1) A coating composition of claim 1, wherein the polyfunctional resin is a polyol. ### Claim 3 (depends on 1) A coating composition of claim 1, wherein the polyfunctional resin is a polyamine. ### Claim 4 A coating crosslinker composition comprising: a polyisocyanate compound; and a 1,1-di-activated vinyl compound, or a multifunctional form thereof, or a combination thereof, wherein the 1,1-di-activated vinyl compound comprises a methylene dicarbonyl compound, a dihaloalkyl disubstituted vinyl compound, a multifunctional form of a methylene dicarbonyl compound, a multifunctional form of a dihaloalkyl compound, a multifunctional form of a dihaloalkyl disubstituted vinyl compound, or combination thereof. ### Claim 5 A multi-layer coating comprising: a first coating layer applied over at least a portion of a substrate; and a second coating layer applied over at least a portion of the first coating layer; wherein the second coating layer comprises: a reaction product of a first polyfunctional resin and a polyisocyanate; and one or more of: an addition reaction product of: a second polyfunctional resin; and a 1,1-di-activated vinyl compound, or a multifunctional form thereof, or a combination thereof; and/or a polymerization reaction product of the 1,1-di-activated vinyl compound, or a multifunctional form thereof, or a combination thereof, wherein the 1,1-di-activated vinyl compound comprises a methylene dicarbonyl compound, a dihaloalkyl disubstituted vinyl compound, a multifunctional form of a methylene dicarbonyl compound, a multifunctional form of a dihaloalkyl compound, a multifunctional form of a dihaloalkyl disubstituted vinyl compound, or combination thereof. ### Claim 6 (depends on 5) A multi-layer coating of claim 5 wherein the first polyfunctional resin, the second polyfunctional resin, or a combination thereof is a polyol. ### Claim 7 (depends on 5) A multi-layer coating of claim 5 wherein the first polyfunctional resin, the second polyfunctional resin, or a combination thereof is a polythiol. ### Claim 8 (depends on 5) A multi-layer coating of claim 5 wherein the first polyfunctional resin, the second polyfunctional resin, or a combination thereof is a polyamine. ### Claim 9 (depends on 5) The multi-layer coating of claim 5, wherein the second coating layer comprises an addition reaction product of: (1) a polyfunctional resin comprising a polyol; and (2) diethyl methylene malonate and a multifunctional form of diethyl methylene malonate, wherein the multifunctional form of diethyl methylene malonate comprises a transesterification adduct of diethyl methylene malonate and at least one polyol. ### Claim 10 (depends on 9) The multi-layer coating of claim 9, wherein the transesterification adduct of diethyl methylene malonate and at least one polyol comprises a transesterification adduct of diethyl methylene malonate and a diol. ### Claim 11 (depends on 5) The multi-layer coating of claim 5, wherein the first coating layer comprises an activator compound that activated addition reactions and/or polymerization reactions in the second coating layer when the second coating layer was applied over the first coating layer. ### Claim 12 (depends on 11) The multi-layer coating of claim 11, wherein the activator compound comprises a tertiary amine compound. ### Claim 13 (depends on 5) The multi-layer coating of claim 5, wherein the second coating layer comprises a clearcoat layer. ### Claim 14 (depends on 5) An article comprising the multi-layer coating of claim 5 deposited on a surface of the article. ### Claim 15 (depends on 14) The article of claim 14, wherein the article comprises a vehicle component or a component of a free-standing structure. ### Claim 16 A process for coating a substrate comprising: applying a first coating layer over at least a portion of a substrate; applying a second coating layer over at least a portion of the first coating layer; and curing the second coating layer; wherein the second coating layer comprises a coating composition comprising: a polyol resin; polyisocyanate; and a 1,1-di-activated vinyl compound, or a multifunctional form thereof, or a combination thereof, wherein the 1,1-di-activated vinyl compound comprises a methylene dicarbonyl compound, a dihaloalkyl disubstituted vinyl compound, a multifunctional form of a methylene dicarbonyl compound, a multifunctional form of a dihaloalkyl compound, a multifunctional form of a dihaloalkyl disubstituted vinyl compound, or combination thereof. ### Claim 17 (depends on 16) The process of claim 16, wherein the curing of the second coating layer comprises a multiple-curing mechanism comprising: crosslinking reactions between the polyol resin and the polyisocyanate; and one or more of: polymerization reactions of the 1,1-di-activated vinyl compound, or a multifunctional form thereof, or a combination thereof; and/or addition reactions between the polyol resin and the 1,1-di-activated vinyl compound, or a multifunctional form thereof, or a combination thereof. ### Claim 18 (depends on 16) The process of claim 16, wherein: the first coating layer comprises an activator compound; the curing of the second coating layer comprises activating a polymerization reaction and/or an addition reaction in the second coating layer with the activator compound in the first coating layer; and the 1,1-di-activated vinyl compound, or a multifunctional form thereof, or a combination thereof (1) is polymerized and/or (2) reacts with the polyol resin to produce an addition reaction product. ### Claim 19 (depends on 18) The process of claim 18, wherein the activator compound comprises a tertiary amine compound. ### Claim 20 (depends on 17) The process of claim 17, wherein the second coating layer, when cured, comprises: a reaction product of the polyol resin and the polyisocyanate; and a polymerization reaction product of diethyl methylene malonate and a multifunctional form of diethyl methylene malonate, wherein the multifunctional form of diethyl methylene malonate comprises a transesterification adduct of diethyl methylene malonate and at least one polyol. ### Claim 21 (depends on 17) The process of claim 17, wherein the second coating layer, when cured, comprises: a reaction product of the polyol resin and the polyisocyanate; and an addition reaction product of: (1) the polyol resin; and (2) diethyl methylene malonate and a multifunctional form of diethyl methylene malonate, wherein the multifunctional form of diethyl methylene malonate comprises a transesterification adduct of diethyl methylene malonate and at least one polyol.