# US 11,897,978 B2 · Hybrid light-curing composition > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,897,978 B2 - Document ID: US11897978B2 - Status: Granted - Kind: B2 - Application number: 17/211,152 - Filed: 2021-03-24 - Published: 2021-09-30 - Granted: 2024-02-13 - Earliest claimed: 2020-03-31 - Assignees: Dymax Corporation - Applicants: Dymax Corporation - Inventors: Ahmet Nebioglu; Aysegul Kascatan Nebioglu; Sushanta Das; Keith Plimpton - Web page: https://patentgrep.com/patent/US11897978B2 ## CPC - C08F 20/34: Esters containing nitrogen {, e.g. N,N-dimethylaminoethyl (meth)acrylate} - C08F 222/322: {Alpha-cyano-acrylic acid ethyl ester, e.g. ethyl-2-cyanoacrylate} - C07F 17/02: of metals of Groups 8, 9 or 10 of the Periodic Table - C08F 2/48: by ultraviolet or visible light - C08F 4/32: Organic compounds - C08F 4/42: Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors - C08F 290/067: {Polyurethanes; Polyureas} - C08G 18/168: {Organic compounds} - C08G 18/4233: {derived from polymerised higher fatty acids or alcohols} - C08G 18/425: {the polyols containing one or two ether groups} - C08G 18/4825: {Polyethers containing two hydroxy groups (C08G18/4833 - C08G18/5096 take precedence)} - C08G 18/4854: {Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group} - C08G 18/672: {Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen} - 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 18/758: {containing two or more cycloaliphatic rings} - C08G 18/765: {alpha, alpha, alpha', alpha', -tetraalkylxylylene diisocyanate or homologues substituted on the aromatic ring} - C08K 5/05: Alcohols; Metal alcoholates - C09D 4/00: Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond {; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16} - C09D 175/16: having terminal carbon-to-carbon unsaturated bonds - C09J 4/00: Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond {; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16} - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22) - 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) - 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) - C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H) ## Abstract In an aspect, a curable composition comprises an acid catalyzed urethane (meth)acrylate oligomer comprising an acid catalyst; a cyanoacrylate monomer; a metallocene compound; a free radical polymerization inhibitor; and an acidic anionic polymerization inhibitor. In yet another aspect, a method of making a cured composition comprises forming the curable composition; and curing the curable composition by exposing it to light to form the cured composition. ## Claims ### Claim 1 A curable composition comprising: an acid catalyzed urethane (meth)acrylate oligomer comprising an acid catalyst; a cyanoacrylate monomer; a metallocene compound; a free radical polymerization inhibitor; and an acidic anionic polymerization inhibitor. ### Claim 2 (depends on 1) The curable composition of claim 1, wherein the acid catalyzed urethane (meth)acrylate oligomer has a structure of at least one of Formula (1) or Formula (2): A-D-(PD)n-A (1) A-(PD)n-P-A (2) wherein each A independently is a monohydroxy functional (meth)acrylate group; each D independently is a di- or tri-functional isocyanate group; each P independently is a polyol having a weight average molecular weight of 100 50 to 12,000 Daltons based on polystyrene standards; and n is 1 to 100. ### Claim 3 (depends on 1) The curable composition of claim 1, wherein the acid catalyzed urethane (meth)acrylate oligomer comprises at least one of: a polyester of hexanedioic acid and diethylene glycol, reacted with isophorone diisocyanate, capped with 2-hydroxyethyl (meth)acrylate; a polypropylene glycol reacted with tolyene-2,6-diisocyanate, capped with 2-hydroxyethyl (meth)acrylate; a polyester of hexanedioic acid and diethylene glycol, reacted with 4,4′-methylenebis(cyclohexyl isocyanate), capped with 2-hydroxyethyl (meth)acrylate; a polyester of hexanedioic acid, 1,2-ethanediol, and 1,2 propanediol, reacted with tolylene-2,4-diisocyanate, capped with 2-hydroxyethyl (meth)acrylate; a polyester of hexanedioic acid, 1,2-ethanediol, and 1,2 propanediol, reacted with 4,4′-methylenebis(cyclohexyl isocyanate), capped with 2-hydroxyethyl (meth)acrylate; a polyester of hexanedioic acid, diethylene glycol, reacted with isophorone diisocyanate, capped with 2-hydroxyethyl (meth)acrylate; a polytetramethylene glycol ether reacted with 4,4′-methylenebis(cyclohexylisocyanate), capped with 2-hydroxyethyl (meth)acrylate; or a polypropylene glycol reacted with tetramethylxylene diisocyanate, capped with 2-hydroxyethyl (meth)acrylate. ### Claim 4 (depends on 1) The curable composition of claim 1, wherein the curable composition comprises 0.1 to 30 wt % of the acid catalyzed urethane (meth)acrylate based on the total weight of the curable composition. ### Claim 5 (depends on 1) The curable composition of claim 1, wherein the acid catalyst comprises at least one of a nonmetallic Lewis acid or an organic acid. ### Claim 6 (depends on 1) The curable composition of claim 1, wherein the acid catalyst is present in an amount of 0.05 to 6 wt % based on the total weight of the urethane(meth)acrylate oligomer. ### Claim 7 (depends on 1) The curable composition of claim 1, wherein the cyanoacrylate monomer has the structure wherein R is a C1-15 alkyl, alkoxy alkyl, cycloalkyl, alkenyl, aralkyl, aryl, allyl, or haloalkyl group. ### Claim 8 (depends on 1) The curable composition of claim 1, wherein the cyanoacrylate monomer comprises at least one of methyl cyanoacrylate, ethyl-2-cyanoacrylate, propyl cyanoacrylate, butyl cyanoacrylate, octyl cyanoacrylate, allyl-2-cyanoacrylate, or β-methoxyethyl-2-cyanoacrylate. ### Claim 9 (depends on 1) The curable composition of claim 1, wherein the curable composition comprises 20 to 98 wt % of the cyanoacrylate monomer based on the total weight of the curable composition. ### Claim 10 (depends on 1) The curable composition of claim 1, wherein the metallocene compound comprises at least one of ferrocene or a titanocene. ### Claim 11 (depends on 1) The curable composition of claim 1, wherein the metallocene compound is present in an amount of 0.005 to 4 wt % based on the total weight of the curable composition. ### Claim 12 (depends on 1) The curable composition of claim 1, wherein the free radical polymerization inhibitor comprises at least one of hydroquinone, catechol, beta-naphthol, mono-t-butylhydroquinone, pyrogallol, 4-methoxy phenol, 4-tert-butylphenol, 2,5-di-tert-butylhydroquinone, or 2,6-di-tertbutyl-4-methylphenol. ### Claim 13 (depends on 1) The curable composition of claim 1, wherein the free radical polymerization inhibitor is present in an amount of 0.001 to 1 wt % based on the total weight of the curable composition. ### Claim 14 (depends on 1) The curable composition of claim 1, wherein the acidic anionic polymerization inhibitor comprises at least one of a lewis acid, a carboxylic acid, or a sulfonic acid. ### Claim 15 (depends on 1) The curable composition of claim 1, wherein the acidic anionic polymerization inhibitor is present in an amount of 0.001 to 1 wt % based on the total weight of the curable composition. ### Claim 16 (depends on 1) A cured composition derived from claim 1. ### Claim 17 (depends on 1) An article or a coating comprising the cured composition of claim 1, wherein the article can be a medical device, an electronic device, or a nail. ### Claim 18 A curable composition comprising: 0.1 to 30 wt % of an acid catalyzed urethane (meth)acrylate oligomer having a structure of at least one of Formula (1) or Formula (2) that was made with 0.05 to 6 wt % of an acid catalyst based on the total weight of the urethane (meth)acrylate oligomer: A-D-(PD)n-A (1) A-(PD)n-P-A (2) wherein each A independently is a monohydroxy functional (meth)acrylate group; each D independently is derived from a di- or tri-functional isocyanate group; each P independently is derived from a polyol having a weight average molecular weight of 50 to 12,000 Daltons based on polystyrene standards; and n is 10 to 100; 20 to 98 wt % of a cyanoacrylate monomer; 0.005 to 4 wt % of a metallocene compound; 0.001 to 1 wt % of a free radical polymerization inhibitor; and 0.01 to 0.1 wt % of an acidic anionic polymerization inhibitor. ### Claim 19 (depends on 18) The curable composition of claim 18, wherein the acid catalyst comprises at least one of a nonmetallic Lewis acid or an organic acid; the cyanoacrylate monomer comprises at least one of methyl cyanoacrylate, ethyl-2-cyanoacrylate, propyl cyanoacrylate, butyl cyanoacrylate, octyl cyanoacrylate, allyl-2-cyanoacrylate, or β-methoxyethyl-2-cyanoacrylate; the metallocene compound comprises at least one of ferrocene or a titanocene; wherein the free radical polymerization inhibitor comprises at least one of hydroquinone, catechol, beta-naphthol, mono-t-butylhydroquinone, pyrogallol, 4-methoxy phenol, 4-tert-butylphenol, 2,5-di-tert-butylhydroquinone, or 2,6-di-tertbutyl-4-methylphenol; and the acidic anionic polymerization inhibitor comprises at least one of a lewis acid, a carboxylic acid, or a sulfonic acid. ### Claim 20 A method of making a cured composition comprising: curing a curable composition by exposing it to light to form the cured composition; wherein the curable composition comprises an acid catalyzed urethane (meth)acrylate oligomer comprising an acid catalyst; a cyanoacrylate monomer; a metallocene compound; a free radical polymerization inhibitor; and an acidic anionic polymerization inhibitor.