Claims
- 1. A compound of formula (I) or (II)
- 2. A compound according to claim 1 of formula IA or IIA
- 3. A compound according to claim 1 of formula IA
- 4. A compound according to claim 1 wherein T1 and T2 are independently alkylene of 2 or 3 carbon atoms.
- 5. A compound according to claim 1 wherein R1 and R2 are independently alkyl of 1 to 6 carbon atoms or phenyl.
- 6. A compound of formula I according to claim 1 which is
(a) 5-trifluoromethyl-2-[2-hydroxy-3-(3-triethoxysilyl)propyl-5-tert-octylphenyl]-2H-benzotriazole; (b) 5-trifluoromethyl-2-{2-hydroxy-3-tert-butyl-5-[3-(3-triethyoxysilyl)propylcarbamoyloxy)-propyl]phenyl}2H-benzotriazole; (c) 5-trifluoromethyl-2-{2-hydroxy-3-tert-butyl-5-[2-(3-triethyoxysilyl)propylcarbamoyl-oxy)ethyl]phenyl}2H-benzotriazole; (d) 5-trifluoromethyl-2-{2-hydroxy-5-[2-(3-triethyoxysilyl)propyl-carbamoyloxy)ethyl]-phenyl}2H-benzotriazole; (e) 5-trifluoromethyl-2-{2-hydroxy-3-α-cumyl-5-[2-(3-triethyoxysilyl)propylcarbamoyl-oxy)ethyl]phenyl}-2H-benzotriazole; (f) 5-trifluoromethyl-2-{2-hydroxy-3-tert-butyl-5-[2-(3-(diethoxymethylsilyl)propylamino-carbonylethyl]phenyl}2H-benzotriazole; (g) 5-phenylsulfonyl-2-{2-hydroxy-3-tert-butyl-5-[3-(2-ethoxydimethylsilyl)ethylcarbonyl-oxy)propyl]phenyl}2H-benzotriazole; (h) 5-n-butylsulfonyl-2-{2-hydroxy-3-tert-butyl-5-[2-(3-ethoxydimethylsilyl)propyl-oxycarbonyl)ethyl]phenyl}2H-benzotriazole; (i) 5-trifluoromethyl-2-[2-hydroxy-3-(ethoxydimethylsilyl)propyl-5-tert-octylphenyl]-2H-benzotriazole; (j) 5-trifluoromethyl-2-[2-hydroxy-3-(trimethylsilyl)propyl-5-tert-butylphenyl]-2H-benzotriazole; (k) 5-[3-(diethoxyethylsilyl)propoxycarbonyl]-2-(2-hydroxy-3-α-cumyl-5-tert-octyl-phenyl)-2H-benzotriazole; (l) 5-[3-(diethoxyethylsilyl)propylaminocarbonyl]-2-(2-hydroxy-3-α-cumyl-5-tert-octyl-phenyl)-2H-benzotriazole; 37
- 7. A composition stabilized against light-induced degradation which comprises
(a) an organic material subject to light-induced degradation, and (b) an effective stabilizing amount of a compound of formula (I) or (II) according to claim 1.
- 8. A composition according to claim 7 wherein component (a) is a natural, semi-synthetic or synthetic polymer.
- 9. A composition according to claim 8 wherein the polymer is a thermoplastic polymer.
- 10. A composition according to claim 7 wherein the polymer is a polyolefin or Polycarbonate.
- 11. A composition according to claim 10 wherein the polymer is polyethylene or polypropylene.
- 12. A composition according to claim 7 wherein the polymer is polypropylene; or the polymer is a styrenic, ABS, a nylon, a polyester such as poly(ethylene terephthalate) or poly(butylene terephthalate), a polyurethane, an acrylate, a rubber modified styrenic, poly(vinyl chloride), poly(vinyl butyral), polyacetal (polyoxymethylene), poly(ethylene naphthalene-dicarboxylate), or other blends or copolymers such as poly(ethylene/1,4-cyclohexylene-dimethylene terephthalate) PETG or an ionomer.
- 13. A composition according to claim 8 wherein the polymer is a siloxane coating as a screening layer over polycarbonate.
- 14. A composition according to claim 7 wherein the organic material of component (a) is a resin selected from the group consisting of a thermoset acrylic melamine resin, an acrylic urethane resin, an epoxy carboxy resin, a silane modified acrylic melamine, an acrylic resin with carbamate pendant groups crosslinked with melamine or an acrylic polyol resin crosslinked with melamine containing carbamate groups.
- 15. A composition according to claim 7 wherein the organic material of component (a) is a acrylosilane coating useful in organosilicone hardcoats or softcoats for automotive applications such as GENIVA (DuPont) coatings or for multilayered compositions.
- 16. A composition according to claim 7 which additionally contains as coadditive a phenolic antioxidant selected from the group consisting of n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate), di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 3,6-dioxaoctamethylene bis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate), 2,6-di-tert-butyl-p-cresol, 2,2′-ethylidene-bis(4,6-di-tert-butylphenol), 1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl)isocynurate, 1,1,3,-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris-[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanurate, 3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine, N,N′-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate), ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, and N,N′-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]-oxamide.
- 17. A composition according to claim 7 which additionally contains as coadditive a hindered amine selected from the group consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, di(1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triaza-spiro[4.5]decane-2,4-dione, tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate, 1,2-bis(2,2,6,6-tetramethyl-3-oxopiperazin4-yl)ethane, 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodispiro[5.1.11.2]heneicosane, polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine), polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, polycondensation product of 4,4′-hexamethylenebis-(amino-2,2,6,6-tetramethylpiperidine) and 1,2-dibromoethane, tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) 1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl) 1,2,3,4-butanetetracarboxylate, polycondensation product of 2,4-dichloro-6-morpholino-s-triazine and 4,4′-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine), N,N′, N″, N′″-tetrakis[(4,6-bis(butyl-1,2,2,6,6-pentamethylpiperidin-4-yl)-amino-s-triazin-2-y l]-1,10-diamino4,7-diazadecane, mixed [2,2,6,6-tetramethylpiperidin-4-yl/β,β,β′,β′-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5.5]-undecane) diethyl]1,2,3,4-butanetetracarboxylate, mixed [1,2,2,6,6-pentamethylpiperidin-4-yl/β,β,β′,α′-tetramethyl-3,9-(2,4 ,8,10-tetraoxaspiro[5.5]undecane)diethyl] 1,2,3,4-butanetetracarboxylate, octamethylene bis(2,2,6,6-tetramethylpiperidin-4-carboxylate), 4,4′-ethylenebis(2,2,6,6-tetramethylpiperazin-3-one), N-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide, N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecylsuccinimide, N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide, 1-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate, I-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine, poly-[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1 -cyclohexyloxy-2,2,6,6-tetramethyl-piperidin-4-yl)imino], 2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine, and 1-(2-hydroxy-2-ethylpropoxy-4-octadecanoyloxy-2,2,6,6-tetramethyl-piperidine.
- 18. A composition according to claim 7 which additionally contains as coadditive another UV absorber selected from the group consisting of the benzotriazoles, s-triazines, the oxanilides, the benzylidene malonates the hydroxybenzophenones, benzoates and α-cyanoacrylates.
- 19. A composition according to claim 18 wherein the UV absorber is a 2-hydroxyphenyl-2H-benzotriazole selected from the group consisting of
2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole; 2-[2-hydroxy-3,5-di(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole; 2-[2-hydroxy-3-(α,α-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole; 2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]phenyl}-2H-benzotriazole; 5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole; 5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole; 2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole; 2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H- benzotriazole; 5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-octylphenyl)-2H-benzotriazole; 5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole; 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole; 2,2′-methylene-bis[6-(5-trifluoromethyl-2H-benzotriazol-2-yl)-4-tert-octylphenol]; methylene-2-[4-tert-octyl-6-(2H-benzotriazol-2-yl)phenol]2′-[4-tert-octyl-6-(5-trifluoro-methyl-2H-benzotriazol-2-yl)phenol]; 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamic acid; methyl 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate; isooctyl 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate; 5-trifluoromethyl-2-[2-hydroxy-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole; 5-trifluoromethyl-2-[2-hydroxy-5-(3-acryloyloxypropyl)phenyl]-2H-benzotriazole; 5-trifluoromethyl-2-[2-hydroxy-5-(3-methacryloyloxypropyl)phenyl]-2H-benzotriazole; 5-trifluoromethyl-2-[2-hydroxy-5-(3-acrylyaminopropyl)phenyl]-2H-benzotriazole; 5-trifluoromethyl-2-[2-hydroxy-5-(3-methacrylylaminopropyl)phenyl]-2H-benzotriazole; 5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-tert-butylphenyl)-2H-benzotriazole; 5-trifluoromethyl-2-(2-hydroxy-3-α-cumyl-5-nonylphenyl)-2H-benzotriazole; 5-trifluoromethyl-2-[2-hydroxy-3-α-cumyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole; 5-trifluoromethyl-2-[2-hydroxy-3-α-cumyl-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole; 5-trifluoromethyl-2-(2-hydroxy-3,5-ditert-amylphenyl)-2H-benzotriazole; 5-trifluoromethyl-2-(2-hydroxy-3,5-ditert-butylphenyl)-2H-benzotriazole; 5-trifluoromethyl-2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole; 5-Trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(3-hydroxypropyl)phenyl)-2H-benzotriazole; 5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole; 5-trifluoromethyl-2-[2-hydroxy-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole; 5-trifluoromethyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole; 5-fluoro-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole; 5-butylsulfonyl-2-(2-hydroxy-3,5-di-α-cumylphenyl)-2H-benzotriazole; 5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole; and 5-butylsulfonyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole.
- 20. A composition according to claim 18 wherein the UV absorber is a tris-aryl-s-triazine is selected from the group consisting of
2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine; 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine; and 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hydroxypropoxy)-phenyl]-s-triazine.
- 21. A composition stabilized against light-induced degradation which comprises an ultraviolet light screening layer over a solid substrate, wherein the screening layer comprises a silicone coating and at least one compound selected from the group consisting of compounds of formuae (I) and (II) according to claim 1.
- 22. A composition according to claim 21, in which the solid substrate is polycarbonate.
- 23. A composition according to claim 22, wherein the compounds of formulae (I) and (II) are selected from the group consisting of
(a) 5-trifluoromethyl-2-[2-hydroxy-3-(3-triethoxysilyl)propyl-5-tert-octylphenyl]-2H-benzotriazole; (b) 5-trifluoromethyl-2-{2-hydroxy-3-tert-butyl-5-[3-(3-triethyoxysilyl)propylcarbamoyloxy)-propyl]phenyl}2H-benzotriazole; (c) 5-trifluoromethyl-2-{2-hydroxy-3-tert-butyl-5-[2-(3-triethyoxysilyl)propylcarbamoyl-oxy)ethyl]phenyl}-2H-benzotriazole; (d) 5-trifluoromethyl-2-{2-hydroxy-5-[2-(3-triethyoxysilyl)propyl-carbamoyloxy)ethyl]-phenyl}2H-benzotriazole; (e) 5-trifluoromethyl-2-{2-hydroxy-3-α-cumyl-5-[2-(3-triethyoxysilyl)propylcarbamoyl-oxy)ethyl]phenyl}-2H-benzotriazole; (f) 5-trifluoromethyl-2-{2-hydroxy-3-tert-butyl-5-[2-(3-(diethoxymethylsilyl)propylamino-carbonylethyl]phenyl}2H-benzotriazole; (g) 5-phenylsulfonyl-2-{2-hydroxy-3-tert-butyl-5-[3-(2-ethoxydimethylsilyl)ethylcarbonyl-oxy)propyl]phenyl}2H-benzotriazole; (h) 5-n-butylsulfonyl-2-{2-hydroxy-3-tert-butyl-5-[2-(3-ethoxydimethylsilyl)propyl-oxycarbonyl)ethyl]phenyl}2H-benzotriazole; (i) 5-trifluoromethyl-2-[2-hydroxy-3-(ethoxydimethylsilyl)propyl-5-tert-octylphenyl]-2H-benzotriazole; (j) 5-trifluoromethyl-2-[2-hydroxy-3-(trimethylsilyl)propyl-5-tert-butylphenyl]-2H-benzotriazole; (k) 5-[3-(diethoxyethylsilyl)propoxycarbonyl]-2-(2-hydroxy-3-α-cumyl-5-tert-octyl-phenyl)-2H-benzotriazole; (l) 5-[3-(diethoxyethylsilyl)propylaminocarbonyl]-2-(2-hydroxy-3-α-cumyl-5-tert-octyl-phenyl)-2H-benzotriazole; 38
Parent Case Info
[0001] This application claims the benefit under 35 USC 119(e) of U.S. Provisional Application Serial Nos. 60/222,783, filed Aug. 3, 2000 and 60/303,048, filed Jul. 5, 2001.
[0002] The instant invention pertains to photostable, silylated benzotriazole UV absorbers and compositions stabilized therewith. These benzotriazole compounds are novel and exhibit enhanced durability due to either the incorporation of electron withdrawing moieties at the 5-position of the benzo ring or to the presence of an α-cumyl group on the phenol ring. The polymer compositions containing said benzotriazoles are advantageously stabilized, especially high performance coatings such as organopolysiloxanes. The instant compounds are red-shifted and show increased absorption in the 350-400 nm region of the UV spectrum.
Provisional Applications (2)
|
Number |
Date |
Country |
|
60222783 |
Aug 2000 |
US |
|
60303048 |
Jul 2001 |
US |