# US 5,708,048 A · Radiation curable hardcoat compositions > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,708,048 A - Document ID: US5708048A - Status: Granted - Kind: A - Application number: 08/694,224 - Filed: 1996-08-08 - Granted: 1998-01-13 - Earliest claimed: 1992-06-25 - Assignees: General Electric Company - Inventors: George Fredric Medford; Gautam Patel - Web page: https://patentgrep.com/patent/US5708048A ## CPC - 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: 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) ## Abstract A radiation (UV or E-beam) curable hardcoat composition formed of a mixture of colloidal silica and hydrolyzed silica acrylate, an acrylic monomer and a photoinitiator is disclosed. Additives including a hindered amine light stabilizer, a fluoroacrylate and alkyl acrylate are employed to improve cure, clarity and hardness. A diphenyl (2,4,6-trimethyl(benzoyl) phosphine oxide UV initiator causes effective out of focus curing. ## Claims ### Claim 1 A method substantially free of a solvent strip step for making a radiation curable hardcoat composition consisting essentially of the steps: (1) agitating a mixture of (i) water miscible alcohol, (ii) colloidal silica, component (A), and (iii) a silyl acrylate having the formula: ##STR11## which upon hydrolysis produces component (B); (2) hydrolyzing and condensing the mixture from step (1) resulting in a product; (3) adding to the product of step (2) a monomer or a blend of monomers, component (C), having the formula: ##STR12## wherein in said silyl acrylate and in said monomer, R is a one to thirteen carbon atom monovalent hydrocarbon radical, R.sup.1 is a one to eight carbon atom alkyl radical, R.sup.2 is selected from the group consisting of hydrogen, R and mixtures thereof, R.sup.3 is a one to eight carbon atom alkylene radical, R.sup.4 is selected from the group consisting of branched two to eight carbon atom alkylene radicals, branched two to eight carbon atom halogenated alkylene radicals, branched two to eight carbon atom hydroxylated alkylene radicals, branched acrylate radicals, six to thirteen carbon atom arylene radicals, halogenated six to thirteen carbon atom arylene radicals and R.sup.3, R.sup.5 has at least one carbon atom and may have the formula: --C(R.sup.2).sub.2 --CHR.sup.2 R.sup.3 --, where a is a whole number equal to 0-2 inclusive, b is an integer ranging from 1 to 3 inclusive, the sum of a+b ranges from 1 to 3 inclusive and n is an integer ranging from 1 to 6 inclusive; (4) adding a diphenyl(2, 4, 6-trimethyl(benzoyl))phosphine oxide, component (D), ultraviolet photoinitiator; (5) adding poly(methylmethacrylate/butylmethacrylate), component (G); and (6) optionally adding a hindered amine light stabilizer, component (E), a fluoroacrylate, component (F), or an ultraviolet (UV) absorber (A) or mixtures thereof. ### Claim 2 (depends on 1) The method according to claim 1, wherein Component (E) is added in an amount up to 0.5 parts by weight based upon (A), (B), (C) and (D). ### Claim 3 (depends on 1) The method according to claim 1, wherein Component (F) is added in an amount up to 1.25 parts by weight based upon (A), (B), (C) and (D). ### Claim 4 (depends on 1) The method according to claim 1, wherein Component (G) is added in an amount up to 10.0 parts by weight based upon (A), (B), (C) and (D). ### Claim 5 (depends on 4) The method according to claim 4, wherein said water miscible alcohol comprises less than 50% of the resulting mixture of (4). ### Claim 6 (depends on 1) The method according to claim 1, wherein the silyl acrylate is .gamma.-methacryloxypropyl trimethoxysilane. ### Claim 7 (depends on 1) The method according to claim 1, wherein the acrylic monomer is a mixture of hexanedioldiacrylate dipentaerythritorpentaacrylate, octylacrylate and decylacrylate. ### Claim 8 (depends on 1) The method according to claim 1, wherein the water miscible alcohol is methoxypropanol, or isopropyl alcohol or blends of methoxypropanol and isopropyl alcohol. ### Claim 9 (depends on 1) The method according to claim 1, wherein at least one UV absorber is present. ### Claim 10 (depends on 9) The method according to claim 9, wherein said UV absorber is an acrylate modified 2,4-dihydroxy benzophenone. ### Claim 11 (depends on 1) The method according to claim 1 wherein at least one ultraviolet absorber is added to the resulting mixture of (3). ### Claim 12 (depends on 1) The method according to claim 1, wherein said water miscible alcohol comprises less than 50% of the resulting mixture of (4). ### Claim 13 (depends on 1) The process of claim 1 wherein a hindered amine light stabilizer, component (E), or a fluoroacrylate, component (F), or a mixture of both is added. ### Claim 14 (depends on 1) A method comprising the method according to claim 1, the step of applying the resulting mixture of (6) to a substrate thereby producing an applied composition, and the step of exposing the applied composition to an ultraviolet light source. ### Claim 15 A radiation curable hardcoat composition consisting essentially of: (1) a mixture of (i) water miscible alcohol, (ii) colloidal silica, component (A), and (iii) a silyl acrylate having the formula: ##STR13## which upon hydrolysis produces component (B); (2) a acrylic monomer or a blend of acrylic monomers, component (C), having the formula: ##STR14## wherein in said silyl acrylate and in said monomer, R is a one to thirteen carbon atom monovalent hydrocarbon radical, R.sup.1 is a one to eight carbon atom alkyl radical, R.sup.2 is selected from the group consisting of hydrogen, R and mixtures thereof, R.sup.3 is a one to eight carbon atom alkylene radical, R.sup.4 is selected from the group consisting of branched two to eight carbon atom alkylene radicals, branched two to eight carbon atom halogenated alkylene radicals, branched two to eight carbon atom hydroxylated alkylene radicals, branched acrylate radicals, six to thirteen carbon atom arylene radicals, halogenated six to thirteen carbon atom arylene radicals and R.sup.3, R.sup.5 has at least one carbon atom and may have the formula: --C(R.sup.2).sub.2 --CHR.sup.2 R.sup.3 --, where a is a whole number equal to 0-2 inclusive, b is an integer ranging from 1 to 3 inclusive, the sum of a+b ranges from 1 to 3 inclusive and n is an integer ranging from 1 to 6 inclusive; (3) a diphenyl(2, 4, 6-trimethyl(benzoyl))phosphine oxide, component (D), ultraviolet photoinitiator; (4) a poly(methylmethacrylate/butylmethacrylate), component (G); and (5) optionally a hindered amine light stabilizer, component (E), a fluoroacrylate, component (F), or an ultraviolet absorber or mixtures thereof. ### Claim 16 (depends on 15) The composition according to claim 15, wherein component (E), of a hindered amine light stabilizer, is present in an amount ranging up to about 2.0 parts by weight based upon components (A), (B), (C) and (D). ### Claim 17 (depends on 15) The composition according to claim 15, wherein Component (E) is present in an amount ranging from about 0.125 to about 2.5 parts by weight based upon Components (A), (B), (C) and (D). ### Claim 18 (depends on 15) The composition according to claim 15, wherein component (F), a fluoroacrylate, is present in an amount ranging up to about 1.25 parts by weight based upon Components (A), (B), (C) and (D). ### Claim 19 (depends on 18) The composition according to claim 18, wherein Component (F) is present in an amount ranging from about 0.06 to about 0.125 parts by weight based upon Components (A), (B), (C) and (D). ### Claim 20 (depends on 15) The composition according to claim 15, wherein component (G) is present in an amount ranging up to about 10.0 parts by weight based upon components (A), (B), (C) and (D). ### Claim 21 (depends on 15) The composition according to claim 15, wherein Component (G) is present in an amount ranging from about 1.0 to about 5.0 parts by weight based upon Components (A), (B), (C) and (D). ### Claim 22 (depends on 15) The composition according to claim 15, wherein said water miscible alcohol is methoxypropanol or isopropyl alcohol or blends thereof. ### Claim 23 (depends on 22) The composition according to claim 22, wherein said miscible alcohol is less than 50% of the resulting mixtures of (A), (B), (C) and (D). ### Claim 24 (depends on 15) The composition according to claim 15, further comprising between 2 and 22 parts by weight ultraviolet absorbers based on (A), (B) and (C). ### Claim 25 (depends on 15) The composition according to claim 15, wherein the silyl acrylate is .gamma.-methacryloxypropyl trimethoxysilane. ### Claim 26 (depends on 15) The composition according to claim 15, wherein the acrylic monomer is a mixture of hexanedioldiacrylate, dipentaerythritolpentaacrylate, octylacrylate, and decylacrylate. ### Claim 27 A radiation curable hardcoat composition consisting essentially of: (1) a mixture of (i) water miscible alcohol, (ii) colloidal silica, component (A), and (iii) a silyl acrylate having the formula: ##STR15## which upon hydrolysis produces component (B); (2) a acrylic monomer or a blend of acrylic monomers, component (C), having the formula: ##STR16## wherein in said silyl acrylate and in said monomer, R is a one to thirteen carbon atom monovalent hydrocarbon radical, R.sup.1 is a one to eight carbon atom alkyl radical, R.sup.2 is selected from the group consisting of hydrogen, R and mixtures thereof, R.sup.3 is a one to eight carbon atom alkylene radical, R.sup.4 is selected from the group consisting of branched two to eight carbon atom alkylene radicals, branched two to eight carbon atom halogenated alkylene radicals, branched two to eight carbon atom hydroxylated alkylene radicals, branched acrylate radicals, six to thirteen carbon atom arylene radicals, halogenated six to thirteen carbon atom arylene radicals and R.sup.3, R.sup.5 has at least one carbon atom and may have the formula: --C(R.sup.2).sub.2 --CHR.sup.2 R.sup.3 --, where a is a whole number equal to 0-2 inclusive, b is an integer ranging from 1 to 3 inclusive, the sum of a+b ranges from 1 to 3 inclusive and n is an integer ranging from 1 to 6 inclusive wherein the total of components (A), (B), and (C) equals 100 parts by weight; (3) a diphenyl(2, 4, 6-trimethyl(benzoyl))phosphine oxide, component (D), ultraviolet photoinitiator; (4) a poly(methylmethacrylate/butylmethacrylate), component (G); and (5) optionally a hindered amine light stabilizer, component (E), a fluoroacrylate, component (F), or an ultraviolet absorber or mixtures thereof.