Claims
- 1. A composition stabilized against the deleterious effects of actinic radiation which comprises
- (a) a polymer subject to degradation when exposed to actinic radiation, and
- (b) an effective stabilizing amount of a compound of formula I ##STR13## wherein G.sub.1 is a group of the formula ##STR14## G.sub.2 is a group of the formula ##STR15## where q is 0 or 1,
- R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10 are independently of one another hydrogen, hydroxyl, cyano, alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, cycloalkyl of 4 to 12 carbon atoms, cycloalkoxy of 4 to 12 carbon atoms, halogen, haloalkyl of one to 5 carbon atoms, sulfonyl, carboxyl, acylamino of 2 to 12 carbon atoms, acyloxy of 2 to 12 carbon atoms, alkoxycarbonyl of 2 to 12 carbon atoms, aminocarbonyl, or R.sub.3 and R.sub.4 together with the phenyl radical to which they are attached, are a cyclic radical interrupted by one or more oxygen or nitrogen atoms,
- E.sub.2 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms or cycloalkyl of 5 to 12 carbon atoms; or said alkyl or cycloalkyl substituted by one to eight halogen, epoxy, glycidyloxy, furyloxy, --E.sub.4, --OE.sub.5, --N(E.sub.5).sub.2, --CON(E.sub.5).sub.2, --COE.sub.5, --COOE.sub.5, --OCOE.sub.5, --OCOC(E.sub.5).dbd.C(E.sub.5).sub.2, --C(E.sub.5).dbd.CCOOE.sub.5, --CN, --NCO, or ##STR16## combination thereof; or said alkyl or cycloakyl interrupted by one to six epoxy, --O--, --NE.sub.5 --, --CONE.sub.5 --, --COO--, --OCO--,--CO--, --C(E.sub.5).dbd.C(E.sub.5)COO--, --OCOC(E.sub.5).dbd.C(E.sub.5)--, --(E.sub.5)C.dbd.C(E.sub.5)--, phenylene, or -phenylene-G.sub.3 -phenylene in which G.sub.3 is --O--, --S--, --SO.sub.2 --, --CH.sub.2 --, or --C(CH.sub.3).sub.2 --, or combinations thereof; or said alkyl or cycloalkyl both substituted and interrupted by combinations of the groups mentioned above; or E.sub.2 is --SO.sub.2 E.sub.3, or --COE.sub.6 ;
- E.sub.4 is aryl of 6 to 10 carbon atoms, or said aryl substituted by one to three halogen alkyl of 1 to 8 carbon atoms, or combinations thereof; cycloalkyl of 5 to 12 carbon atoms; or phenylalkyl of 7 to 15 carbon atoms, or said phenylalkyl substituted on the phenyl ring by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combination thereof; or straight or branched chain alkenyl of 2 to 18 carbon atoms;
- E.sub.5 is defined as E.sub.4, or E.sub.5 is also hydrogen or straight or branched chain alkyl of 1 to 24 carbon atoms or E.sub.5 is a group of the formula ##STR17## where T.sub.1 is hydrogen, oxyl, hydroxyl, alkyl of 1 to 12 carbon atoms, said alkyl substituted by at least one hydroxyl or lower alkoxy, benzyl or alkanoyl of 2 to 18 carbon atoms,
- E.sub.6 is straight or branched chain alkyl of 1 to 18 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, phenyl, alkoxy of 1 to 12 carbon atoms, phenoxy, alkylamino of 1 to 12 carbon atoms, arylamino of 6 to 12 carbon atoms or a group --E.sub.7 COOH or --NH--E.sub.8 --NCO;
- E.sub.7 is alkylene of 2 to 14 carbon atoms or o-phenylene;
- E.sub.8 is alkylene of 2 to 10 carbon atoms, phenylene, tolylene, diphenylenemethane or a group ##STR18## t is 0 to 9; and L is straight or branched chain alkylene of 1 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms, alkylene by or interrupted by cyclohexylene or phenylene; or L is benzylidene; or L is --S--, --S--S--, --S--L.sub.1 --S--, --SO--, --SO.sub.2 --, --SO--L.sub.1 --SO--, --SO.sub.2 --L.sub.1 --SO.sub.2 --, --CH.sub.2 --NH--L.sub.1 --NH--CH.sub.2 -- or ##STR19## where L.sub.1 is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms, or alkylene interrupted or terminated by cyclohexylene of 8 to 12 carbon atoms; with the proviso that at least one L linkage is attached to the phenyl ring in the 5-position.
- 2. A composition according to claim 1 where in formula I,
- G.sub.1 and G.sub.2 are biphenyl substituted with one to three lower alkyl or halogen;
- E.sub.2 is straight or branched chain alkyl of 2 to 24 carbon atoms, or said alkyl substituted by one or two --OE.sub.5, where E.sub.5 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, or phenyl.
- 3. A composition according to claim 2 where in formula I,
- E.sub.2 is alkyl of 2 to 24 carbon atoms substituted by one hydroxyl and by one --OE.sub.5 where E.sub.5 is alkyl of 1 to 24 carbon atoms or phenyl.
- 4. A composition according to claim 1 where in formula I,
- G.sub.1 and G.sub.2 are biphenylyl substituted with one to three lower alkyl or halogen;
- t is 0 to 3; and
- L is methylene; benzylidene; ##STR20##
- 5. A composition according to claim 1 where in formula I,
- G.sub.1 and G.sub.2 are 4-biphenylyl;
- E.sub.2 is straight or branched chain alkyl of 2 to 6 carbon atoms, or said alkyl substituted by one or two --OE.sub.5 where E.sub.5 is hydrogen or straight or branched chain alkyl of 1 to 24 carbon atoms.
- 6. A composition according to claim 5 where in formula I, E.sub.2 is alkyl of 1 to 24 carbon atoms substituted by one hydroxyl and by one alkoxy of 1 to 24 carbon atoms.
- 7. A composition according to claim 1 wherein the compound of formula I is
- a. 1,3-bis{1-�2,4-dihydroxy-5-(3,5-di(4-biphenylyl)-s-triazinyl))phenyl!-1-methyl-ethyl}benzene;
- b. mixture of methylene-bis-�2-(2-hydroxy-4-octyloxyphenyl)-4,6-di(4-biphenylyl)-s-triazine bridged in the 3:5, 5:5 and 3:3 position in a 5:4:1 ratio; and
- c. mixture of benzylidene-bis-�2-(2-hydroxy-4-octyloxyphenyl)-4,6-di(4-biphenylyl)-s-triazine!; bridged in the 3:5 and 5:5 position in a 1:1 ratio.
- 8. A composition according to claim 7 wherein the compound of formula I is
- b. mixture of methylene-bis-2-(2-hydroxy-4-octyloxyphenyl)-4,6-di(4-biphenylyl)-s-triazine; bridged in the 3:5, 5:5 and 3:3 position in a 5:4:1 ratio.
- 9. A composition according to claim 1 wherein the polymer is a high solids thermoset acrylic/melamine resin or an acrylic urethane resin.
- 10. A composition according to claim 9 wherein the polymer is a high solids thermoset acrylic/melamine resin.
- 11. A composition according to claim 1 where the composition is a polymer film composition which comprises
- (a) an electro coat primer in adhesion to a metal substrate,
- (b) a base or color coat that is in adhesion to the electro coat and which comprises a film-forming binder and an organic pigment or an inorganic pigment or mixtures thereof,
- (c) a clear coat that is in adhesion to the base coat and which comprises a film-forming binder, and
- (d) an effective stabilizing amount, of at least one tris-aryl-s-triazine UV absorber contained in either the base coat or the clear coat or both base coat and clear coat.
- 12. A composition according to claim 11 wherein component (d) is between 1 and 20% by weight of the film-forming binder.
- 13. A composition according to claim 11 wherein component (d) is incorporated into the base coat.
- 14. A composition according to claim 11 which additionally contains an effective stabilizing amount of at least one 2-hydroxyphenyl-2H-benzotriazole; another tris-aryl-s-triazine; or hindered amine light stabilizer or mixtures thereof.
- 15. A composition according to claim 14 wherein the 2-hydroxyphenyl-2H-benzotriazole is selected from the group consisting of
- 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;
- 2-�2-hydroxy-3,5-di(.alpha.,.alpha.-dimethylbenzyl)phenyl!-2H-benzotriazole
- 2-�2-hydroxy-3-(.alpha.,.alpha.-dimethylbenzyl)-5-octylphenyl!-2H-benzotriazole;
- 2-{2-hydroxy-3-tert-butyl-5-�2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl!-phenyl}-2H-benzotriazole; and
- 2-{2-hydroxy-3-tert-butyl-5-�2-(octyloxy)carbonyl)ethyl!phenyl}-2H-benzotriazole.
- 16. A composition according to claim 14 wherein the other 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-hydroxy-propoxy)phenyl!-s-triazine.
- 17. A composition according to claim 14 which contains an effective amount of hindered amine light stabilizer.
- 18. A composition according to claim 17 wherein the hindered amine is 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-oxopiperazin-4-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-2,2,6,6-tetramethylpiperidin-4-yl)-amino-s-triazin-2-yl!-1,10-diamino-4,7-diazadecane,
- mixed �2,2,6,6-tetramethylpiperidin-4-yl/.beta.,.beta.,.beta.',.beta.'-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/.beta.,.beta.,.beta.',.beta.'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro�5.5!undecane)diethyl! 1,2,3,4-butanetetracarboxylate,
- octamethylene bis(2,2,6,6-tetramethylpiperidin4-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-acetyl3-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,
- 1-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-tetramethylpiperidin-4-yl)imino!, and
- 2,4,6-tris�N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino!-s-triazine.
- 19. A composition according to claim 17 wherein the hindered amine is
- 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,
- the polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxy-piperidine and succinic acid,
- the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),
- N,N',N",N'"-tetrakis�(4,6-bis(butyl-(2,2,6,6-tetramethylpiperidin-4-yl)amino)-s-triazine-2-yl!-1,10-diamino-4,7-diazadecane,
- di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,
- di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate,
- 1-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-tetramethylpiperidin-4-yl)imino!, or
- 2,4,6-tris�N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino!-s-triazine.
- 20. A composition according to claim 11 wherein the film-forming binder is a high solids thermoset acrylic/melamine resin.
- 21. A composition according to claim 11 wherein the film-forming binder is an acrylic urethane resin.
Parent Case Info
This is a divisional of application Ser. No. 08/703,751, filed on Aug. 27, 1996, which is now U.S. Pat. No. 5,726,309, issued on Mar. 10, 1998.
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Foreign Referenced Citations (8)
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Dec 1985 |
EPX |
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Divisions (1)
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Number |
Date |
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Parent |
703751 |
Aug 1996 |
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