Benzotriazole UV absorbers having enhanced durability
First Claim
1. A compound of formula I, III or IV ##STR13## wherein G1 is hydrogen or chloro,G2 is cyano, perfluoroalkyl of 1 to 12 carbon atoms or fluoro,G6 is perfluoroalkyl of 1 to 12 carbon atoms,G7 is hydrogen or perfluoroalkyl of 1 to 12 carbon atoms,E1 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms;
- or E1 is alkyl of 1 to 24 carbon atoms substituted by one or two hydroxy groups,E2 and E2 '"'"' are independently straight or branched alkyl chain of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by one to three alkyl of 1 to 4 carbon atoms;
or E2 and E2 '"'"' are independently said alkyl of 1 to 24 carbon atoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more --OH, --OCOE11, --OE4, --NCO, --NH2, --NHCOE11, --NHE4 or --N(E4)2, or mixtures thereof, where E4 is straight or branched chain alkyl of 1 to 24 carbon atoms;
or said alkyl or said alkenyl interrupted by one or more --O--, --NH-- or --NE4 -- groups or mixtures thereof and which can be unsubstituted or substituted by one or more --OH, --OE4 or --NH2 groups or mixtures thereof;
n is 1 or 2,when n is 1, E5 is OE6 or NE7 E8, orE5 is --PO(OE12)2, --OSi(E11)3 or --OCO--E11, or straight or branched chain C1 -C24 alkyl which is interrupted by --O--, --S-- or --NE11 and which can be unsubstituted or substituted by --OH or --OCO--E11, C5 -C12 cycloalkyl which is unsubstituted or substituted by --OH, straight chain or branched C2 -C18 alkenyl which is unsubstituted or substituted by --OH, C7 -C15 aralkyl, --CH2 --CHOH--E13 or glycidyl,E6 is hydrogen, straight or branched chain C1 -C24 alkyl which is unsubstituted or substituted by one or more OH, OE4 or NH2 groups, or --OE6 is --(OCH2 CH2)w OH or --(OCH2 CH2)w OE21 where w is 1 to 12 and E21 is alkyl of 1 to 12 carbon atoms,E7 and E8 are independently hydrogen, alkyl of 1 to 18 carbon atoms, straight or branched chain C3 -C18 alkyl which is interrupted by --O--, --S-- or --NE11 --, C5 -C12 cycloaLkyl, C6 -C14 aryl or C1 -C3 hydroxylalkyl, or E7 and E8 together with the N atom are a pyrrolidine, piperidine, piperazine or morpholine ring,E5 is --X--(Z)p --Y--E15whereinX is --O-- or --N(E16)--,Y is --O-- or --N(E17)--,Z is C2 -C12 -alkylene, C4 -C12 -alkylene interrupted by one to three nitrogen atoms, oxygen atoms or a mixture thereof, or is C3 -C12 -alkylene, butenylene, butynylene, cyclohexylene or phenylene, each substituted by a hydroxyl group,m is zero, 1 or 2,p is 1, or p is also zero when X and Y are --N(E16)-- and --N(E17)--, respectively,E15 is a group --CO--C(E18)═
C(H)E19 or, when Y is --N(E17)--, forms together with E17 a group --CO--CH═
CH--CO--, wherein E18 is hydrogen or methyl, and E19 is hydrogen, methyl or --CO--X--E20, wherein E20 is hydrogen, C1 -C12 -alkyl or a group of the formula ##STR14## wherein the symbols E1, G2, X, Z, m and p have the meanings defined above, and E16 and E17 independently of one another are hydrogen, C1 -C12 -alkyl, C3 -C12 -alkyl interrupted by 1 to 3 oxygen atoms, or is cyclohexyl or C7 -C15 aralkyl, and E16 together with E17 in the case where Z is ethylene, also forms ethylene,when n is 2, E5 is one of divalent radicals --O--E9 --O-- or --N(E11)--E10 --N(E11)--,E9 is C2 -C8 alkylene, C4 -C8 alkenylene, C4 alkynylene, cyclohexylene, straight or branched chain C4 -C10 alkylene which is interrupted by --O-- or by --CH2 --CHOH--CH2 --O--E14 --O--CH2 --CHOH--CH2 --,E10 being straight or branched chain C2 -C12 alkylene which may be interrupted by --O--, cyclohexylene, or ##STR15## or E10 and E11 with the two nitrogen atoms form a piperazine ring,E14 is straight or branched chain C2 -C8 alkylene, straight or branched chain C4 -C10 alkylene which is interrupted by --O--, cycloalkylene, arylene or ##STR16## where E7 and E8 are independently hydrogen, alkyl of 1 to 18 carbon atoms or E7 and E8 together are alkylene of 4 to 6 carbon atoms, 3-oxapentamethylene, 3-iminopentamethylene or 3-methyliminopentamethylene,E11 is hydrogen, straight or branched chain C1 -C18 alkyl, C5 -C12 cycloalkyl, straight or branched chain C2 -C18 alkenyl, C6 -C14 aryl or C7 -C15 aralkyl,E12 is straight or branched chain C1 -C18 alkyl, straight or branched chain C3 -C18 alkenyl, C5 -C10 cycloalkyl, C6 -C16 aryl or C7 -C15 aralkyl,E13 is H, straight chain or branched C1 -C18 alkyl which is substituted by --PO(OE12)2, phenyl which is unsubstituted or substituted by OH, C7 -C15 aralkyl or --CH2 OE12,L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbon atoms, benzylidene, p-xylylene, α
,α
,α
'"'"',α
'"'"'-tetramethyl-m-xylylene or cycloalkylidene, andwith the proviso that when G2 is CF3 and E1 is hydrogen, E2 is not methyl.
1 Assignment
0 Petitions
Accused Products
Abstract
Benzotriazole UV absorbers which are substituted at the 5-position of the benzo ring by an electron withdrawing group exhibit enhanced durability and very low loss rates when incorporated into automotive coatings. This is particularly the case when the 3-position of the phenyl ring is also substituted by phenyl or phenylalkyl such as α-cumyl. Compounds where the 5-position of the benzo ring are substituted by perfluoroalkyl such as trifluoromethyl are particularly of interest for both their enhanced durability and for their excellent solubility and excellent color properties in some thermoplastic compositions when the phenyl ring is substituted at the 3-position by hydrogen or tert-alkyl.
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Citations
8 Claims
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1. A compound of formula I, III or IV ##STR13## wherein G1 is hydrogen or chloro,
G2 is cyano, perfluoroalkyl of 1 to 12 carbon atoms or fluoro, G6 is perfluoroalkyl of 1 to 12 carbon atoms, G7 is hydrogen or perfluoroalkyl of 1 to 12 carbon atoms, E1 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms; - or E1 is alkyl of 1 to 24 carbon atoms substituted by one or two hydroxy groups,
E2 and E2 '"'"' are independently straight or branched alkyl chain of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by one to three alkyl of 1 to 4 carbon atoms;
or E2 and E2 '"'"' are independently said alkyl of 1 to 24 carbon atoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more --OH, --OCOE11, --OE4, --NCO, --NH2, --NHCOE11, --NHE4 or --N(E4)2, or mixtures thereof, where E4 is straight or branched chain alkyl of 1 to 24 carbon atoms;
or said alkyl or said alkenyl interrupted by one or more --O--, --NH-- or --NE4 -- groups or mixtures thereof and which can be unsubstituted or substituted by one or more --OH, --OE4 or --NH2 groups or mixtures thereof;n is 1 or 2, when n is 1, E5 is OE6 or NE7 E8, or E5 is --PO(OE12)2, --OSi(E11)3 or --OCO--E11, or straight or branched chain C1 -C24 alkyl which is interrupted by --O--, --S-- or --NE11 and which can be unsubstituted or substituted by --OH or --OCO--E11, C5 -C12 cycloalkyl which is unsubstituted or substituted by --OH, straight chain or branched C2 -C18 alkenyl which is unsubstituted or substituted by --OH, C7 -C15 aralkyl, --CH2 --CHOH--E13 or glycidyl, E6 is hydrogen, straight or branched chain C1 -C24 alkyl which is unsubstituted or substituted by one or more OH, OE4 or NH2 groups, or --OE6 is --(OCH2 CH2)w OH or --(OCH2 CH2)w OE21 where w is 1 to 12 and E21 is alkyl of 1 to 12 carbon atoms, E7 and E8 are independently hydrogen, alkyl of 1 to 18 carbon atoms, straight or branched chain C3 -C18 alkyl which is interrupted by --O--, --S-- or --NE11 --, C5 -C12 cycloaLkyl, C6 -C14 aryl or C1 -C3 hydroxylalkyl, or E7 and E8 together with the N atom are a pyrrolidine, piperidine, piperazine or morpholine ring, E5 is --X--(Z)p --Y--E15 wherein X is --O-- or --N(E16)--, Y is --O-- or --N(E17)--, Z is C2 -C12 -alkylene, C4 -C12 -alkylene interrupted by one to three nitrogen atoms, oxygen atoms or a mixture thereof, or is C3 -C12 -alkylene, butenylene, butynylene, cyclohexylene or phenylene, each substituted by a hydroxyl group, m is zero, 1 or 2, p is 1, or p is also zero when X and Y are --N(E16)-- and --N(E17)--, respectively, E15 is a group --CO--C(E18)═
C(H)E19 or, when Y is --N(E17)--, forms together with E17 a group --CO--CH═
CH--CO--, wherein E18 is hydrogen or methyl, and E19 is hydrogen, methyl or --CO--X--E20, wherein E20 is hydrogen, C1 -C12 -alkyl or a group of the formula ##STR14## wherein the symbols E1, G2, X, Z, m and p have the meanings defined above, and E16 and E17 independently of one another are hydrogen, C1 -C12 -alkyl, C3 -C12 -alkyl interrupted by 1 to 3 oxygen atoms, or is cyclohexyl or C7 -C15 aralkyl, and E16 together with E17 in the case where Z is ethylene, also forms ethylene,when n is 2, E5 is one of divalent radicals --O--E9 --O-- or --N(E11)--E10 --N(E11)--, E9 is C2 -C8 alkylene, C4 -C8 alkenylene, C4 alkynylene, cyclohexylene, straight or branched chain C4 -C10 alkylene which is interrupted by --O-- or by --CH2 --CHOH--CH2 --O--E14 --O--CH2 --CHOH--CH2 --, E10 being straight or branched chain C2 -C12 alkylene which may be interrupted by --O--, cyclohexylene, or ##STR15## or E10 and E11 with the two nitrogen atoms form a piperazine ring, E14 is straight or branched chain C2 -C8 alkylene, straight or branched chain C4 -C10 alkylene which is interrupted by --O--, cycloalkylene, arylene or ##STR16## where E7 and E8 are independently hydrogen, alkyl of 1 to 18 carbon atoms or E7 and E8 together are alkylene of 4 to 6 carbon atoms, 3-oxapentamethylene, 3-iminopentamethylene or 3-methyliminopentamethylene, E11 is hydrogen, straight or branched chain C1 -C18 alkyl, C5 -C12 cycloalkyl, straight or branched chain C2 -C18 alkenyl, C6 -C14 aryl or C7 -C15 aralkyl, E12 is straight or branched chain C1 -C18 alkyl, straight or branched chain C3 -C18 alkenyl, C5 -C10 cycloalkyl, C6 -C16 aryl or C7 -C15 aralkyl, E13 is H, straight chain or branched C1 -C18 alkyl which is substituted by --PO(OE12)2, phenyl which is unsubstituted or substituted by OH, C7 -C15 aralkyl or --CH2 OE12, L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbon atoms, benzylidene, p-xylylene, α
,α
,α
'"'"',α
'"'"'-tetramethyl-m-xylylene or cycloalkylidene, andwith the proviso that when G2 is CF3 and E1 is hydrogen, E2 is not methyl. - View Dependent Claims (2, 3, 4, 5, 6, 7, 8)
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4. A compound according to claim 1 of formula IV wherein
G6 is CF3, G7 is hydrogen or CF3, E2 and E2 '"'"' are independently straight or branched alkyl chain of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3 alkyl of 1 to 4 carbon atoms; - and
L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbon atoms, benzylidene, p-xylylene, α
,α
,α
'"'"',α
'"'"'-tetramethyl-m-xylylene or cycloalkylidene.
- and
-
5. A compound according to claim 1 of formula I ##STR20## wherein G1 is hydrogen,
G2 is CF3 --, E1 is phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms, E2 is straight or branched alkyl chain of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3 alkyl of 1 to 4 carbon atoms; - or E2 is said alkyl of 1 to 24 carbon atoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more --OH, --OCOE11, --NH2 or --NHCOE11, or mixtures thereof, or said alkyl or said alkenyl interrupted by one or more --O-- and which can be unsubstituted or substituted by one or more --OH, or
is a compound of formula I wherein, G1 is hydrogen, G2 is CF3 --, E1 is hydrogen, straight or branched alkyl of 4 to 24 carbon atoms or phenylalkyl of 7 to 15 carbon atoms, and E2 is as defined above.
- or E2 is said alkyl of 1 to 24 carbon atoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more --OH, --OCOE11, --NH2 or --NHCOE11, or mixtures thereof, or said alkyl or said alkenyl interrupted by one or more --O-- and which can be unsubstituted or substituted by one or more --OH, or
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6. A compound according to claim 1 of formula III ##STR21## wherein G1 is hydrogen,
G2 is CF3 --, E1 is hydrogen, straight or branched alkyl of 4 to 24 carbon atoms or phenylalkyl of 7 to 15 carbon atoms, E5 is --OE6 or --NE7 E8 where E6 is hydrogen, straight or branched chain C1 -C24 alkyl which is unsubstituted or substituted by one or more OH groups, or --OE6 is --(OCH2 CH2)w OH or --(OCH2 CH2)w OE21 where w is 1 to 12 and E21 is alkyl of 1 to 12 carbon atoms, and E7 and E8 are independently hydrogen, alkyl of 1 to 18 carbon atoms, straight or branched chain C3 -C18 alkyl which is interrupted by --O--, --S-- or --NE11 --, C5 -C12 cycloalkyl, C6 -C14 aryl or C1 -C3 hydroxylalkyl, or E7 and E8 together with the N atom are a pyrrolidine, piperidine, piperazine or morpholine ring. -
7. A compound according to claim 1 of formula IV ##STR22## wherein G6 is CF3,
G7 is hydrogen or CF3, E2 and E2 '"'"' are independently straight or branched alkyl chain of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3 alkyl of 1 to 4 carbon atoms; - and
L is methylene.
- and
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8. A compound according to claim 1 which is
(a) 5-trifluoromethyl-2-(2-hydroxy-3-α - -cumyl-5-tert-octylphenyl)-2H-benzotriazole;
(b) 5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole; (c) 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole; (d) 2,2'"'"'-methylene-bis[6-(5-trifluoromethyl-2H-benzotriazol-2-yl)-4-tert-octyl-phenol]; (e) methylene-2-[4-tert-octyl-6-(2H-benzotriazol-2-yl)phenol]2'"'"'-[4-tert-octyl-6-(5-trifluoromethyl-2H-benzotriazol-2-yl)phenol]; (f) 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamic acid; (g) methyl 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate; (h) isooctyl 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate; (i) 5-trifluoromethyl-2-[2-hydroxy-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole (j) 5-trifluoromethyl-2-[2-hydroxy-5-(3-acryloyloxypropyl)phenyl]-2H-benzotriazole; (k) 5-trifluoromethyl-2-[2-hydroxy-5-(3-methacryloyloxypropyl)phenyl]-2H-benzotriazole; (l) 5-trifluoromethyl-2-[2-hydroxy-5-(3-acrylylaminopropyl)phenyl]-2H-benzotriazole; (m) 5-trifluoromethyl-2-[2-hydroxy-5-(3-methacrylylaminopropyl)phenyl]-2H-benzotriazole; (n) 5-trifluoromethyl-2-(2-hydroxy-3-α
-cumyl-5-tert-butylphenyl)-2H-benzotriazole;(o) 5-trifluoromethyl-2-(2-hydroxy-3-α
-cumyl-5-nonylphenyl)-2H-benzotriazole;(p) 5-trifluoromethyl-2-[2-hydroxy-3-α
-cumyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;(q) 5-trifluoromethyl-2-[2-hydroxy-3-α
-cumyl-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole;(r) 5-trifluoromethyl-2-(2-hydroxy-3,5-ditert-amylphenyl)-2H-benzotriazole; (s) 5-trifluoromethyl-2-(2-hydroxy-3,5-ditert-butylphenyl)-2H-benzotriazole; (t) 5-trifluoromethyl-2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole; (u) 5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(3-hydroxypropyl)phenyl)-2H-benzotriazole; (v) 5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole; (w) 5-trifluoromethyl-2-[2-hydroxy-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole; (x) 5-trifluoromethyl-2-(2-hydroxy-3,5-di-α
-cumylphenyl)-2H-benzotriazole;
or(y) 5-fluoro-2-(2-hydroxy-3,5-di-α
-cumylphenyl)-2H-benzotriazole.
- -cumyl-5-tert-octylphenyl)-2H-benzotriazole;
- or E1 is alkyl of 1 to 24 carbon atoms substituted by one or two hydroxy groups,
Specification