U.S. patent application number 09/760089 was filed with the patent office on 2001-07-12 for benzotriazole uv absorbers having enhanced durability.
Invention is credited to Debellis, Anthony, Detlefsen, Robert E., Iyengar, Revathi, Ravichandran, Ramanathan, Suhadolnik, Joseph, Wolf, Jean-Pierre, Wood, Mervin G..
Application Number | 20010007886 09/760089 |
Document ID | / |
Family ID | 22883195 |
Filed Date | 2001-07-12 |
United States Patent
Application |
20010007886 |
Kind Code |
A1 |
Ravichandran, Ramanathan ;
et al. |
July 12, 2001 |
Benzotriazole UV absorbers having enhanced durability
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.
Inventors: |
Ravichandran, Ramanathan;
(Nanuet, NY) ; Suhadolnik, Joseph; (Yorktown
Heights, NY) ; Wood, Mervin G.; (Poughquag, NY)
; Debellis, Anthony; (Garnerville, NY) ;
Detlefsen, Robert E.; (Putnam Valley, NY) ; Iyengar,
Revathi; (Courtland Manor, NY) ; Wolf,
Jean-Pierre; (Courtaman, CH) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION
PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
22883195 |
Appl. No.: |
09/760089 |
Filed: |
January 11, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09760089 |
Jan 11, 2001 |
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09614527 |
Jul 12, 2000 |
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09614527 |
Jul 12, 2000 |
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09234880 |
Jan 21, 1999 |
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6166218 |
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09234880 |
Jan 21, 1999 |
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08961127 |
Oct 30, 1997 |
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5977219 |
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Current U.S.
Class: |
524/91 |
Current CPC
Class: |
B41M 5/124 20130101;
B41M 5/3375 20130101; C09D 7/48 20180101; C08K 5/3475 20130101;
C07F 9/65188 20130101; B41M 5/392 20130101; C07D 249/20 20130101;
Y10S 430/132 20130101 |
Class at
Publication: |
524/91 |
International
Class: |
C08K 005/3475 |
Claims
What is claimed is:
1. A coating composition, stabilized with a benzotriazole, which
benzotriazole exhibits enhanced durability and a low loss rate when
incorporated in said coating, which composition comprises (a) 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, and (b) 0.01
to 5% by weight, based on resin solids, of a benzotriazole of
formula A, B, C or D 13wherein G.sub.1, G.sub.2 or T is an electron
withdrawing radical, G.sub.1 is hydrogen or halogen, G.sub.2 is
halogen, nitro, cyano, R.sub.3SO--, R.sub.3SO.sub.2--,
--COOG.sub.3, CF.sub.3--, --P(O)(C.sub.6H.sub.5).sub.2- ,
--CO--G.sub.3, --CO--NH--G.sub.3, --CO--N(G.sub.3).sub.2,
--N(G.sub.3)--CO--G.sub.3, 14G.sub.3 is hydrogen, straight or
branched chain alkyl of 1 to 24 carbon atoms, straight of 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 4 alkyl
of 1 to 4 carbon atoms, R.sub.1 is hydrogen, straight or branched
chain alkyl of 1 to 24 carbon atoms, straight of 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 4 alkyl
of 1 to 4 carbon atoms, R.sub.2 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 R.sub.2 is hydroxyl or --OR.sub.4 where R.sub.4 is
straight or branched chain alkyl of 1 to 24 carbon atoms; or said
alkyl substituted by one or more --OH, --OCO--R.sub.11, --OR.sub.4,
--NCO or --NH.sub.2 groups or mixtures thereof; or said alkyl or
said alkenyl interrupted by one or more --O--, --NH-- or
--NR.sub.4-- groups or mixtures thereof and which can be
unsubstituted or substituted by one or more --OH, --OR.sub.4 or
--NH.sub.2 groups or mixtures thereof; or R.sub.2 is --SR.sub.3,
--NHR.sub.3 or --N(R.sub.3).sub.2; or R.sub.2 is
(CH.sub.2).sub.m--CO--X-- -(Z).sub.p--Y--R.sub.15 wherein X is
--O-- or --N(R.sub.16)--, Y is --O-- or --N(R.sub.17)--, Z is
C.sub.2-C.sub.12-alkylene, C.sub.4-C.sub.12-alkylene interrupted by
one to three nitrogen atoms, oxygen atoms or a mixture thereof, or
is C.sub.3-C.sub.12-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(R.sub.16)-- and
--N(R.sub.17)--, respectively, R.sub.15 is a group
--CO--C(R.sub.18).dbd.C(H)R.sub.19 or, when Y is --N(R.sub.17)--,
forms together with R.sub.17 a group --CO--CH.dbd.CH--CO--, wherein
R.sub.18 is hydrogen or methyl, and R.sub.19 is hydrogen, methyl or
--CO--X--R.sub.20, wherein R.sub.20 is hydrogen,
C.sub.1-C.sub.12-alkyl or a group of the formula. 15wherein the
symbols R.sub.1, R.sub.3, X, Z, m and p have the meanings defined
above, and R.sub.16 and R.sub.17 independently of one another are
hydrogen, C.sub.1-C.sub.12-alkyl, C.sub.3-C.sub.12-alkyl
interrupted by 1 to 3 oxygen atoms, or is cyclohexyl or
C.sub.7-C.sub.15aralkyl, and R.sub.16 together with R.sub.17 in the
case where Z is ethylene, also forms ethylene, n is 1 or 2, when n
is 1, R.sub.5 is Cl, OR.sub.6 or NR.sub.7R.sub.8, or R.sub.5 is
--PO(OR.sub.12).sub.2, --OSi(R.sub.11).sub.3 or --OCO--R.sub.11, or
straight or branched chain C.sub.1-C.sub.24alkyl which is
interrupted by --O--, --S-- or --NR.sub.11 and which can be
unsubstituted or substituted by --OH or --OCO--R.sub.11,
C.sub.5-C.sub.12 cycloalkyl which is unsubstituted or substituted
by --OH, straight chain or branched C.sub.2-C.sub.18alkenyl which
is unsubstituted or substituted by --OH, C.sub.7-C.sub.15aralkyl,
--CH.sub.2--CHOH--R.sub.13 or glycidyl, R.sub.6 is hydrogen,
straight or branched chain C.sub.1-C.sub.24alkyl which is
unsubstituted or substituted by one or more OH, OR.sub.4 or
NH.sub.2 groups, or --OR.sub.6 is --(OCH.sub.2CH.sub.2).sub.wOH or
--(OCH.sub.2CH.sub.2).sub.wOR.sub.21 where w is 1 to 12 and
R.sub.21 is alkyl of 1 to 12 carbon atoms, R.sub.7 and R.sub.8 are
independently hydrogen, alkyl of 1 to 18 carbon atoms, straight or
branched chain C.sub.3-C.sub.18alkyl which is interrupted by --O--,
--S-- or --NR.sub.11--, C.sub.5-C.sub.12cycloalkyl,
C.sub.6-C.sub.14aryl or C.sub.1-C.sub.3hydroxylalkyl, or R.sub.7
and R.sub.8 together with the N atom are a pyrrolidine, piperidine,
piperazine or morpholine ring, when n is 2, R.sub.5 is one of
divalent radicals --O--R.sub.9--O-- or
--N(R.sub.11)--R.sub.10--N(R.sub.11)--, R.sub.9 is
C.sub.2-C.sub.8alkylene, C.sub.4-C.sub.8alkenylene,
C.sub.4alkynylene, cyclohexylene, straight or branched chain
C.sub.4-C.sub.10alkylene which is interrupted by --O-- or by
--CH.sub.2--CHOH--CH.sub.2--O--R.sub.14--O--
-CH.sub.2--CHOH--CH.sub.2--, R.sub.10 being straight or branched
chain C.sub.2-C.sub.12alkylene which may be interrupted by --O--,
cyclohexylene, or 16or R.sub.10 and R.sub.11 with the two nitrogen
atoms form a piperazine ring, R.sub.14 is straight or branched
chain C.sub.2-C.sub.8alkylene, straight or branched chain
C.sub.4-C.sub.10alkylene which is interrupted by --O--,
cycloalkylene, arylene or 17where R.sub.7 and R.sub.8 are
independently hydrogen, alkyl of 1 to 18 carbon atoms or R.sub.7
and R.sub.8 together are alkylene of 4 to 6 carbon atoms,
3-oxapentamethylene, 3-iminopentamethylene or
3-methyliminopentamethylene, R.sub.11 is hydrogen, straight or
branched chain C.sub.1-C.sub.18alkyl, C.sub.5-C.sub.12cycloalkyl,
straight or branched chain C.sub.3-C.sub.8alkenyl,
C.sub.6-C.sub.14aryl or C.sub.7-C.sub.15aralkyl, R.sub.12 is
straight or branched chain C.sub.1-C.sub.18alkyl, straight or
branched chain C.sub.3-C.sub.18alkenyl- ,
C.sub.5-C.sub.10cycloalkyl, C.sub.6-C.sub.16aryl or
C.sub.7-C.sub.15aralkyl, R.sub.13 is H, straight chain or branched
C.sub.1-C.sub.18alkyl which is substituted by
--PO(OR.sub.12).sub.2, phenyl which is unsubstituted or substituted
by OH, C.sub.7-C.sub.15aralkyl or --CH.sub.2OR.sub.12, R.sub.3 is
alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbon
atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12
carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10
carbon atoms or said aryl substituted by one or two alkyl of 1 to 4
carbon atoms or 1,1,2,2-tetrahydroperfluoroalk- yl where the
perfluoroalkyl moiety is of 6 to 16 carbon atoms, L is alkylene of
1 to 12 carbon atoms, alkylidene of 2 to 12 carbon atoms,
benzylidene, p-xylylene or cycloalkylidene, and T is --SO--,
--SO.sub.2--, --SO--E--SO--, --SO.sub.2--E--SO.sub.2--, --CO--,
--CO--E--CO--, --COO--E--OCO--, --CO--NG.sub.3--E--NG.sub.3--CO--
or --NG.sub.3--CO--E--CO--NG.sub.3--, where E 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,
which benzotriazole exhibits enhanced durability and low loss rate
values when the coating is exposed to actinic radiation as
witnessed by a loss of less than 0.22 absorbance units after
exposure for 1200 hours, or less than 0.27 absorbance units after
1500 hours exposure, or less than 0.40 absorbance units after 2500
hours exposure in a Xenon-Arc Weather-Ometer.
2. A composition according to claim 1 wherein component (b) is a
compound of formula A' 18wherein G.sub.2 is fluoro, chloro, cyano,
R.sub.3SO.sub.2--, CF.sub.3--, --CO--G.sub.3, --COO--G.sub.3 or
--CO--N(G.sub.3).sub.2 G.sub.3 is alkyl of 1 to 12 carbon atoms,
R.sub.1 is hydrogen, alkyl of 1 to 12 carbon atoms, phenyl,
phenylalkyl of 7 to 15 carbon atoms or said phenyl or said
phenylalkyl substituted on the phenyl ring by 1 or 2 alkyl groups
of 1 to 4 carbon atoms, R.sub.2 is alkyl of 1 to 12 carbon atoms,
phenyl, phenylalkyl of 7 to 15 carbon atoms or
--CH.sub.2CH.sub.2COOG.sub.4 where G.sub.4 is hydrogen, alkyl of 1
to 24 carbon atoms or said alkyl substituted by OH, interrupted by
one to six --O-- atoms or both substituted by OH and interrupted by
one to six --O-- atoms, and R.sub.3 is alkyl of 1 to 18 carbon
atom, aryl of 6 to 10 carbon atoms or said aryl substituted one or
two alkyl of 1 to 4 carbon atoms.
3. A composition according to claim 2 where in the compound of
formula A' G.sub.2 is fluoro, chloro, cyano, R.sub.3SO.sub.2--,
CF.sub.3--, --COO--G.sub.3 or --CO--N(G.sub.3).sub.2, G.sub.3 is
alkyl of 1 to 8 carbon atoms, R.sub.1 is hydrogen, phenyl or
.alpha.-cumyl, R.sub.2 is alkyl of 4 to 12 carbon atoms or phenyl,
and R.sub.3 is phenyl or alkyl of 8 to 12 carbon atoms.
4. A composition according to claim 3 wherein G.sub.2 is
phenyl-SO.sub.2--, octyl-SO.sub.2--, fluoro or CF.sub.3--, R.sub.1
is .alpha.-cumyl or phenyl, and R.sub.2 is tert-butyl or
tert-octyl.
5. A composition according to claim 1 wherein component (a) is a
resin which is a thermoset acrylic melamine resin or an acrylic
urethane resin.
6. A composition according to claim 1 which additionally contains a
stabilizing amount of 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-hydroxyhydrocinnamate), 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-tri-
s(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)isocyanurate,
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]isocyanu-
rate, 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-hy-
droxyanilino)-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-hydroxybenzylphosphonate), 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-hydr-
oxyhydrocinnamoyloxy)-ethyl]-oxamide.
7. A composition according to claim 6 wherein the phenolic
antioxidant is neopentanetetrayl
tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl
3,5-di-tert-butyl-4-hydroxyhydrocinnamate,
1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,
2,6-di-tert-butyl-p-cresol or
2,2'-ethylidene-bis(4,6-di-tert-butylphenol- ).
8. A composition according to claim 1 which additionally contains
an effective stabilizing amount of 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-hydroxybenzy- l)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-tetramethylpiperidi- n-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-hydr- oxypiperidine 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--
pentamethyl-piperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazade-
cane, 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-pentamethylpiper-
idin-4-yl/.beta.,.beta.,.beta.',.beta.'-tetramethyl-3,9-(2,4,8,10-tetraoxa-
spiro[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-dodecy- lsuccinimide,
N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecylsuccinimide,
N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yln-dodecylsuccinimide,
1-acetyl3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-di-
one, 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-tetram-
ethylpiperidin-4-yl)imino-hexamethylene-[
4-(1-cyclohexyloxy-2,2,6,6-tetra- methylpiperidin-4-yl)imino], and
2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tet-
ramethylpiperidin-4-yl)-n-butylamino]-s-triazine.
9. A composition according to claim 8 wherein the hindered amine is
bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate,
bis(1,2,2,6,6-pentamethy- lpiperidin-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-hydroxypiperidine and
succinic acid, the polycondensation product of
2,4-dichloro-6-tert-octyla- mino-s-triazine and
4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperid- ine),
N,N',N",N'"-tetrakis[
(4,6-bis(butyl-(1,2,2,6,6-pentamethyl-piperidi-
n-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-t-
etramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-t-
etramethylpiperidin-4-yl)imino], or
2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6--
tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine.
10. A composition according to claim 1 which additionally contains
another UV absorber selected from the group consisting of the
s-triazines, the oxanilides, the hydroxybenzophenones, benzoates
and the .alpha.-cyanoacrylates.
11. A composition according to claim 10 wherein the composition
additionally contains an s-triazine which is
2,4-bis(2,4-dimethylphenyl)--
6-(2-hydroxy-4-octyloxyphenyl)-s-triazine;
2,4-diphenyl-6-(2-hydroxy-4-hex- yloxyphenyl)-s-triazine;
2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do--
/tri-decyloxy-2-hydroxypropoxy)-phenyl] -s-triazine; or
2-(2-hydroxyethylamino)-4,6-bis
[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-tetra-
methylpiperidin-4-yl)amino]-s-triazine.
12. A compound of formula I, II, III or IV 19wherein G.sub.1 is
hydrogen or halogen, G.sub.2 is cyano, E.sub.3SO--,
E.sub.3SO.sub.2--, --COOG.sub.3, CF.sub.3--,
--P(O)(C.sub.6H.sub.5).sub.2, --CO--G.sub.3, --CO--NHG.sub.3 or
--CO--N(G.sub.3).sub.2, G.sub.3 is straight or branched chain alkyl
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 4 alkyl of 1 to 4 carbon
atoms, E.sub.1 is hydrogen, 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, E.sub.2 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 E.sub.2 is hydroxyl or
--OE.sub.4 where E.sub.4 is straight or branched chain alkyl of 1
to 24 carbon atoms; or said alkyl substituted by one or more --OH,
--OCO--E.sub.11, --OE.sub.4, --NCO or --NH.sub.2 groups or mixtures
thereof; or said alkyl or said alkenyl interrupted by one or more
--O--, --NH-- or --NE.sub.4-- groups or mixtures thereof and which
can be unsubstituted or substituted by one or more --OH, --OE.sub.4
or --NH.sub.2 groups or mixtures thereof; or E.sub.2 is --SE.sub.3,
--NHE.sub.3 or --N(E.sub.3).sub.2; or E.sub.2 is
(CH.sub.2).sub.m--CO--X-- -(Z).sub.p--Y--E.sub.15 wherein X is
--O-- or --N(E.sub.16)--, Y is --O-- or --N(E.sub.17)--, Z is
C.sub.2-C.sub.12-alkylene, C.sub.4-C.sub.12-alkylene interrupted by
one to three nitrogen atoms, oxygen atoms or a mixture thereof, or
is C.sub.3-C.sub.12-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(E.sub.16)-- and
--N(E.sub.17)--, respectively, E.sub.15 is a group
--CO--C(E.sub.18).dbd.C(H)E.sub.19 or, when Y is --N(E.sub.17)--,
forms together with E.sub.17 a group --CO--CH.dbd.CH--CO--, wherein
E.sub.18 is hydrogen or methyl, and E.sub.19 is hydrogen, methyl or
--CO--X--E.sub.20, wherein E.sub.20 is hydrogen,
C.sub.1-C.sub.12-alkyl or a group of the formula. 20wherein the
symbols E.sub.1, G.sub.2, X, Z, m and p have the meanings defined
above, and E.sub.16 and E.sub.17 independently of one another are
hydrogen, C.sub.1-C.sub.12-alkyl, C.sub.3-C.sub.12-alkyl
interrupted by 1 to 3 oxygen atoms, or is cyclohexyl or
C.sub.7-C.sub.15aralkyl, and E.sub.16 together with E.sub.17 in the
case where Z is ethylene, also forms ethylene, n is 1 or 2, when n
is 1, E.sub.5 is Cl, OE.sub.6 or NE.sub.7E.sub.8, or E.sub.5 is
--PO(OE.sub.12).sub.2, --OSi(E.sub.11).sub.3 or --OCO--E.sub.11, or
straight or branched chain C.sub.1-C.sub.24alkyl which is
interrupted by --O--, --S-- or --NE.sub.11 and which can be
unsubstituted or substituted by --OH or --OCO--E.sub.11,
C.sub.5-C.sub.12 cycloalkyl which is unsubstituted or substituted
by --OH, straight chain or branched C.sub.2-C.sub.18alkenyl which
is unsubstituted or substituted by --OH, C.sub.7-C.sub.15aralkyl,
--CH.sub.2--CHOH--E.sub.13 or glycidyl, E.sub.6 is hydrogen,
straight or branched chain C.sub.1-C.sub.24alkyl which is
unsubstituted or substituted by one or more OH, OE.sub.4 or
NH.sub.2 groups, or --OE.sub.6 is --(OCH.sub.2CH.sub.2).sub.wOH or
--(OCH.sub.2CH.sub.2).sub.wOE.sub.21 where w is 1 to 12 and
E.sub.21 is alkyl of 1 to 12 carbon atoms, E.sub.7 and E.sub.8 are
independently hydrogen, alkyl of 1 to 18 carbon atoms, straight or
branched chain C.sub.3-C.sub.18alkyl which is interrupted by --O--,
--S-- or --NE.sub.11--, C.sub.5-C.sub.12cycloalkyl,
C.sub.6-C.sub.14aryl or C.sub.1-C.sub.3hydroxylalkyl, or E.sub.7
and E.sub.8 together with the N atom are a pyrrolidine, piperidine,
piperazine or morpholine ring, when n is 2, E.sub.5 is one of
divalent radicals --O--E.sub.9--O-- or
--N(R.sub.11)--E.sub.10--N(E.sub.11)--, E.sub.9 is
C.sub.2-C.sub.8alkylene, C.sub.4-C.sub.8alkenylene,
C.sub.4alkynylene, cyclohexylene, straight or branched chain
C.sub.4-C.sub.10alkylene which is interrupted by --O-- or by
--CH.sub.2--CHOH--CH.sub.2--O--E.sub.14--O--
-CH.sub.2--CHOH--CH.sub.2--, E.sub.10 being straight or branched
chain C.sub.2-C.sub.12alkylene which may be interrupted by --O--,
cyclohexylene, or 21or E.sub.10 and E.sub.11 with the two nitrogen
atoms form a piperazine ring, E.sub.14 is straight or branched
chain C.sub.2-C.sub.8alkylene, straight or branched chain
C.sub.4-C.sub.10alkylene which is interrupted by --O--,
cycloalkylene, arylene or 22where E.sub.7 and E.sub.8 are
independently hydrogen, alkyl of 1 to 18 carbon atoms or E.sub.7
and E.sub.8 together are alkylene of 4 to 6 carbon atoms,
3-oxapentamethylene, 3-iminopentamethylene or
3-methyliminopentamethylene, E.sub.11 is hydrogen, straight or
branched chain C.sub.1-C.sub.18alkyl, C.sub.5-C.sub.12cycloalkyl,
straight or branched chain C.sub.3-C.sub.8alkenyl,
C.sub.6-C.sub.14aryl or C.sub.7-C.sub.15aralkyl, E.sub.12 is
straight or branched chain C.sub.1-C.sub.18alkyl, straight or
branched chain C.sub.3-C.sub.18alkenyl- ,
C.sub.5-C.sub.10cycloalkyl, C.sub.6-C.sub.16aryl or
C.sub.7-C.sub.15aralkyl, E.sub.13 is H, straight chain or branched
C.sub.1-C.sub.18alkyl which is substituted by
--PO(OR.sub.12).sub.2, phenyl which is unsubstituted or substituted
by OH, C.sub.7-C.sub.15aralkyl or --CH.sub.2OE.sub.12, E.sub.3 is
alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 to 20 carbon
atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12
carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10
carbon atoms or said aryl substituted by one or two alkyl of 1 to 4
carbon atoms or 1,1,2,2-tetrahydroperfluoroalk- yl where the
perfluoroalkyl moiety is of 6 to 16 carbon atoms, L is alkylene of
1 to 12 carbon atoms, alkylidene of 2 to 12 carbon atoms,
benzylidene, p-xylylene or cycloalkylidene, and T is --SO--,
--SO.sub.2--, --SO--E--SO--, --SO.sub.2--E--SO.sub.2--, --CO--,
--CO--E--CO--, --COO--E--OCO-- or
--CO--NG.sub.5--E--NG.sub.5--CO--, where E 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;
G.sub.5 is G.sub.3 or hydrogen, and with the proviso that E.sub.1
is not phenylalkyl when G.sub.2 is E.sub.3SO-- or
E.sub.3SO.sub.2--.
13. A compound according to claim 12 which is a compound of formula
I' 23wherein G.sub.2 is cyano, E.sub.3SO.sub.2--, CF.sub.3--,
--COO--G.sub.3--CO--NHG.sub.3 or --CO--N(G.sub.3).sub.2, G.sub.3 is
alkyl of 1 to 12 carbon atoms, E.sub.1 is hydrogen, phenyl,
phenylalkyl of 7 to 15 carbon atoms or said phenyl or said
phenylalkyl substituted on the phenyl ring by 1 or 2 alkyl groups
of 1 to 4 carbon atoms, E.sub.2 is alkyl of 1 to 12 carbon atoms,
phenyl, phenylalkyl of 7 to 15 carbon atoms or
--CH.sub.2CH.sub.2COOG.sub.4 where G.sub.4 is hydrogen, alkyl of 1
to 24 carbon atoms or said alkyl substituted by OH, interrupted by
one to six --O-- atoms or both substituted by OH and interrupted by
one to six --O-- atoms, E.sub.3 is alkyl of 8 to 18 carbon atom,
aryl of 6 to 10 carbon atoms or said aryl substituted one or two
alkyl of 1 to 4 carbon atoms, and with the proviso that E.sub.1 is
not phenylalkyl when G.sub.2 is E.sub.3SO-- or
E.sub.3SO.sub.2--.
14. A compound according to claim 13 wherein G.sub.2 is cyano,
E.sub.3SO.sub.2--, CF.sub.3--, --CO--G.sub.3 or
--CO--N(G.sub.3).sub.2, G.sub.3 is alkyl of 1 to 8 carbon atoms,
E.sub.1 is hydrogen, phenyl or .alpha.-cumyl, E.sub.2 is alkyl of 4
to 12 carbon atoms, and E.sub.3 is phenyl or octyl, and with the
proviso that E.sub.1 is not .alpha.-cumyl when G.sub.2 is
E.sub.3SO.sub.2--.
15. A compound according to claim 14 wherein G.sub.2 is CF.sub.3--,
E.sub.1 is .alpha.-cumyl, and E.sub.2 is tert-butyl or
tert-octyl.
16. A composition stabilized against thermal, oxidative or
light-induced degradation which comprises, (a) an organic material
subject to thermal, oxidative or light-induced degradation, and (b)
an effective stabilizing amount of a compound of formula I, II, III
or IV according to claim 12.
17. A composition according to claim 16 wherein the organic
material is a natural, semi-synthetic or synthetic polymer.
18. A composition according to claim 17 wherein the polymer is a
thermoplastic polymer.
19. A composition according to claim 18 wherein the polymer is is a
polyolefin or polycarbonate.
20. A composition according to claim 19 wherein the polymer is
polyethylene or polypropylene.
21. A composition according to claim 20 wherein the polymer is
polypropylene.
22. A composition according to claim 16 wherein the organic
material 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.
23. A composition according to claim 22 wherein the resin is a
thermoset acrylic melamine resin or an acrylic urethane resin.
24. A composition according to claim 16 wherein the organic
material is a recording material.
Description
[0001] This application claims the benefit under 35 USC 119(e) of
U.S. application Ser. No. 08/745,146, filed on Nov. 7, 1996, and
converted into a Provisional Application by petition under 37 CFR
1.53(b)(2)(ii), filed on May 23, 1997, and granted on Aug. 7,
1997.
[0002] Benzotriazole UV absorbers being substituted in the benzo
ring by electron withdrawing moieties exhibit enhanced durability
and low loss rates when incorporated into automotive coatings.
BACKGROUND OF THE INVENTION
[0003] The benzotriazoles have long been an important class of UV
absorbers and have gained wide commercial importance and acceptance
for many industrial applications. The prior art is replete with
references to their manufacture and utility. However, as
requirements become ever more stringent and demanding, the search
for still more stable and durable benzotriazoles continues. The
gradual phase out of HAPS solvents, such as xylene, because of
environmental concerns and their replacement with non-HAPS
solvents, such as esters, ethers or ketones, and increased
durability requirements for automotive coatings make this search
more urgent. Indeed, the automotive industry is most concerned
about UVA losses from automotive paints and coatings as seen in the
publication by J. L. Gerlock et al., Proc. 36th Annual Tech. Sym.
(Cleveland Coating Society), May 18, 1993.
[0004] Vysokomol Soedin, Ser. A, 18(3), 553 (1976) describes the
linear dependence of hydrogen bond strength and photostability in
benzotriazoles.
[0005] J. E. Pickett et al., Angew. Makromol. Chem. 232, 229 (1995)
describe the photodegradation of benzotriazole UV absorbers in
poly(methyl methacrylate) films. Structural variation generally
caused only small differences in the rates of degradation unless
the substitution disrupted the intramolecular hydrogen bonds which
are critical for stability. Pickett et al. did not test any
benzotriazoles containing both electron withdrawing and electron
donating groups as in the instant invention.
[0006] The prior art leads one to the conclusion that strengthening
the hydrogen bond leads to a more stable benzotriazole, but does
not teach how this can be accomplished. The instant invention
discloses benzotriazoles which exhibit enhanced durability, but
surprisingly this enhanced durability is not always related to
greater hydrogen bond strength. Indeed, compounds with enhanced
durability often have weaker, not stronger hydrogen bonds
[0007] U.S. Pat. Nos. 4,226,763; 4,278,589; 4,315,848; 4,275,004;
4,347,180; 5,554,760; 5,563,242; 5,574,166 and 5,607,987 describe
selected benzotriazoles, substituted in the 3-position of the
hydroxyphenyl ring by an .alpha.-cumyl group, which show very good
durability in automotive coatings. These benzotriazoles represent
the present state of the art. The instant invention is directed at
preparing benzotriazoles which exhibit still better durability and
low loss rates from the prior art benzotriazoles.
[0008] U.S. Pat. Nos. 5,278,314; 5,280,124; 5,436,349 and 5,516,914
describe red-shifted benzotriazoles. These benzotriazoles are
substituted in the 5-position of the benzo ring by thio ethers,
alkylsulfonyl or phenylsulfonyl moieties. Red-shifting the
benzotriazoles is desirable for spectral reasons. A group at the
5-position which is also electron withdrawing provides additional
benefits in low loss rates and durability as found in the instant
invention.
DETAILS OF THE DISCLOSURE
[0009] The instant invention pertains to benzotriazole UV absorbers
having enhanced stability and durability and a low loss rate when
incorporated into automotive coatings.
[0010] More particularly, the instant invention pertains to a
coating composition, stabilized with a benzotriazole, which
benzotriazole exhibits enhanced durability and a low loss rate when
incorporated in said coating, which composition comprises
[0011] (a) 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, and
[0012] (b) 0.01 to 5% by weight, based on resin solids, of a
benzotriazole of formula A, B, C or D 1
[0013] wherein
[0014] G.sub.1, G.sub.2 or T is an electron withdrawing
radical,
[0015] G.sub.1 is hydrogen or halogen,
[0016] G.sub.2 is halogen, nitro, cyano, R.sub.3SO--,
R.sub.3SO.sub.2--, --COOG.sub.3, CF.sub.3--,
--P(O)(C.sub.6H.sub.5).sub.2, --CO--G.sub.3, --CO--NH--G.sub.3,
--CO--N(G.sub.3).sub.2, --N(G.sub.3)--CO--G.sub.3, 2
[0017] G.sub.3 is hydrogen, straight or branched chain alkyl of 1
to 24 carbon atoms, straight of 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 4 alkyl of 1 to 4 carbon
atoms,
[0018] R.sub.1 is hydrogen, straight or branched chain alkyl of 1
to 24 carbon atoms, straight of 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 4 alkyl of 1 to 4 carbon
atoms,
[0019] R.sub.2 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 R.sub.2 is hydroxyl or --OR.sub.4 where R.sub.4 is
straight or branched chain alkyl of 1 to 24 carbon atoms; or said
alkyl substituted by one or more --OH, --OCO--R.sub.11, --OR.sub.4,
--NCO or --NH.sub.2 groups or mixtures thereof; or said alkyl or
said alkenyl interrupted by one or more --O--, --NH-- or
--NR.sub.4-- groups or mixtures thereof and which can be
unsubstituted or substituted by one or more --OH, --OR.sub.4 or
--NH.sub.2 groups or mixtures thereof; or R.sub.2 is --SR.sub.3,
--NHR.sub.3 or --N(R.sub.3).sub.2; or R.sub.2 is
--(CH.sub.2).sub.m--CO--X--(Z).sub.p--Y--R.sub.15
[0020] wherein
[0021] X is --O-- or --N(R.sub.16)--,
[0022] Y is --O-- or --N(R.sub.17)--,
[0023] Z is C.sub.2-C.sub.12-alkylene, C.sub.4-C.sub.12-alkylene
interrupted by one to three nitrogen atoms, oxygen atoms or a
mixture thereof, or is C.sub.3-C.sub.12-alkylene, butenylene,
butynylene, cyclohexylene or phenylene, each substituted by a
hydroxyl group,
[0024] m is zero, 1 or 2,
[0025] p is 1, or p is also zero when X and Y are --N(R.sub.16)--
and --N(R.sub.17)--, respectively,
[0026] R.sub.15 is a group --CO--C(R.sub.18).dbd.C(H)R.sub.19 or,
when Y is --N(R.sub.17)--, forms together with R.sub.17 a group
--CO--CH.dbd.CH--CO--, wherein R.sub.18 is hydrogen or methyl, and
R.sub.19 is hydrogen, methyl or --CO--X--R.sub.20, wherein R.sub.20
is hydrogen, C.sub.1-C.sub.12-alkyl or a group of the formula.
3
[0027] wherein the symbols R.sub.1, R.sub.3, X, Z, m and p have the
meanings defined above, and R.sub.16 and R.sub.17 independently of
one another are hydrogen, C.sub.1-C.sub.12-alkyl,
C.sub.3-C.sub.12-alkyl interrupted by 1 to 3 oxygen atoms, or is
cyclohexyl or C.sub.7-C.sub.15aralkyl, and R.sub.16 together with
R.sub.17 in the case where Z is ethylene, also forms ethylene,
[0028] n is 1 or 2,
[0029] when n is 1, R.sub.5 is Cl, OR.sub.6 or NR.sub.7R.sub.8,
or
[0030] R.sub.5 is --PO(OR.sub.12).sub.2, --OSi(R.sub.11).sub.3 or
--OCO--R.sub.11, or straight or branched chain
C.sub.1-C.sub.24alkyl which is interrupted by --O--, --S-- or
--NR.sub.11 and which can be unsubstituted or substituted by --OH
or --OCO--R.sub.11, C.sub.5-C.sub.12 cycloalkyl which is
unsubstituted or substituted by --OH, straight chain or branched
C.sub.2-C.sub.18alkenyl which is unsubstituted or substituted by
--OH, C.sub.7-C.sub.15aralkyl, --CH.sub.2--CHOH--R.sub.13 or
glycidyl,
[0031] R.sub.6 is hydrogen, straight or branched chain
C.sub.1-C.sub.24alkyl which is unsubstituted or substituted by one
or more OH, OR.sub.4 or NH.sub.2 groups, or --OR.sub.6 is
--(OCH.sub.2CH.sub.2).sub.wOH or
--(OCH.sub.2CH.sub.2).sub.wOR.sub.2, where w is 1 to 12 and
R.sub.21 is alkyl of 1 to 12 carbon atoms,
[0032] R.sub.7 and R.sub.8 are independently hydrogen, alkyl of 1
to 18 carbon atoms, straight or branched chain
C.sub.3-C.sub.18alkyl which is interrupted by --O--, --S-- or
--NR.sub.11, C.sub.5-C.sub.12cycloalkyl, C.sub.6-C.sub.14aryl or
C.sub.1-C.sub.3hydroxylalkyl, or R.sub.7 and R.sub.8 together with
the N atom are a pyrrolidine, piperidine, piperazine or morpholine
ring,
[0033] when n is 2, R.sub.5 is one of divalent radicals
--O--R.sub.9--O-- or --N(R.sub.11)--R.sub.10--N(R.sub.11)--,
[0034] R.sub.9 is C.sub.2-C.sub.8alkylene,
C.sub.4-C.sub.8alkenylene, C.sub.4alkynylene, cyclohexylene,
straight or branched chain C.sub.4-C.sub.10alkylene which is
interrupted by --O-- or by
--CH.sub.2--CHOH--CH.sub.2--O--R.sub.14--O--CH.sub.2--CHOH--CH.sub.2--,
[0035] R.sub.10 being straight or branched chain
C.sub.2-C.sub.12alkylene which may be interrupted by --O--,
cyclohexylene, or 4
[0036] or R.sub.10 and R.sub.11 with the two nitrogen atoms form a
piperazine ring,
[0037] R.sub.14 is straight or branched chain
C.sub.2-C.sub.8alkylene, straight or branched chain
C.sub.4-C.sub.10alkylene which is interrupted by --O--,
cycloalkylene, arylene or 5
[0038] where R.sub.7 and R.sub.8 are independently hydrogen, alkyl
of 1 to 18 carbon atoms or R.sub.7 and R.sub.8 together are
alkylene of 4 to 6 carbon atoms, 3-oxapentamethylene,
3-iminopentamethylene or 3-methyliminopentamethylene,
[0039] R.sub.11 is hydrogen, straight or branched chain
C.sub.1-C.sub.18alkyl, C.sub.5-C.sub.12cycloalkyl, straight or
branched chain C.sub.3-C.sub.8alkenyl, C.sub.6-C.sub.14aryl or
C.sub.7-C.sub.15aralkyl,
[0040] R.sub.12 is straight or branched chain
C.sub.1-C.sub.18alkyl, straight or branched chain
C.sub.3-C.sub.18alkenyl, C.sub.5-C.sub.10cycloalkyl,
C.sub.6-C.sub.16aryl or C.sub.7-C.sub.15aralkyl,
[0041] R.sub.13 is H, straight chain or branched
C.sub.1-C.sub.18alkyl which is substituted by
--PO(OR.sub.12).sub.2, phenyl which is unsubstituted or substituted
by OH, C.sub.7-C.sub.15aralkyl or --CH.sub.2OR.sub.12,
[0042] R.sub.3 is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2
to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of
5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of
6 to 10 carbon atoms or said aryl substituted by one or two alkyl
of 1 to 4 carbon atoms or 1,1,2,2-tetrahydroperfluoroalkyl where
the perfluoroalkyl moiety is of 6 to 16 carbon atoms,
[0043] L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12
carbon atoms, benzylidene, p-xylylene or cycloalkylidene, and
[0044] T is --SO--, --SO.sub.2--, --SO--E--SO--,
--SO.sub.2--E--SO.sub.2--- , --CO--, --CO--E--CO--,
--COO--E--OCO--, --CO--NG.sub.3--E--NG.sub.3--CO-- - or
--NG.sub.3--CO--E--CO--NG.sub.3--,
[0045] where E 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, which benzotriazole exhibits
enhanced durability and low loss rate values when the coating is
exposed to actinic radiation as witnessed by a loss of less than
0.22 absorbance units after exposure for 1200 hours, or less than
0.27 absorbance units after 1500 hours exposure, or less than 0.40
absorbance units after 2500 hours exposure in a Xenon-Arc
Weather-Ometer.
[0046] Preferably, component (b) is a compound of formula A' 6
[0047] wherein
[0048] G.sub.2 is fluoro, chloro, cyano, R.sub.3SO.sub.2--,
CF.sub.3--, --CO--G.sub.3, --COO--G.sub.3 or
--CO--N(G.sub.3).sub.2
[0049] G.sub.3 is alkyl of 1 to 12 carbon atoms,
[0050] R.sub.1 is hydrogen, alkyl of 1 to 12 carbon atoms, phenyl,
phenylalkyl of 7 to 15 carbon atoms or said phenyl or said
phenylalkyl substituted on the phenyl ring by 1 or 2 alkyl groups
of 1 to 4 carbon atoms,
[0051] R.sub.2 is alkyl of 1 to 12 carbon atoms, phenyl,
phenylalkyl of 7 to 15 carbon atoms or --CH.sub.2CH.sub.2COOG.sub.4
where G.sub.4 is hydrogen, alkyl of 1 to 24 carbon atoms or said
alkyl substituted by OH, interrupted by one to six --O-- atoms or
both substituted by OH and interrupted by one to six --O-- atoms,
and
[0052] R.sub.3 is alkyl of 1 to 18 carbon atom, aryl of 6 to 10
carbon atoms or said aryl substituted one or two alkyl of 1 to 4
carbon atoms.
[0053] Most preferably, in the compound of formula A',
[0054] G.sub.2 is fluoro, chloro, cyano, R.sub.3SO.sub.2--,
CF.sub.3--, --COO--G.sub.3 or --CO--N(G.sub.3).sub.2,
[0055] G.sub.3 is alkyl of 1 to 8 carbon atoms,
[0056] R.sub.1 is hydrogen, phenyl or .alpha.-cumyl,
[0057] R.sub.2 is alkyl of 4 to 12 carbon atoms or phenyl, and
[0058] R.sub.3 is phenyl or alkyl of 8 to 12 carbon atoms.
[0059] Especially preferred are the compounds of formula A' where
G.sub.2 is phenyl--SO.sub.2--, octyl-SO.sub.2--, fluoro or
CF.sub.3--, R.sub.1 is .alpha.-cumyl or phenyl, and R.sub.2 is
tert-butyl or tert-octyl.
[0060] Preferably, the resin is a thermoset acrylic melamine resin
or an acrylic urethane resin.
[0061] Examples of these various radicals are as follow:
[0062] When any of R.sub.1 to R.sub.21 is alkyl, such groups are,
for example, methyl, ethyl, isopropyl, n-butyl, isobutyl,
sec-butyl, tert-butyl, tert-amyl, 2-ethylhexyl, tert-octyl, lauryl,
tert-dodecyl, tridecyl, n-hexadecyl, n-octadecyl and eicosyl; when
any of said radicals is alkenyl, such groups are, for example,
allyl or oleyl; when any of said radicals is cycloalkyl, such
groups are, for example, cyclopentyl, cyclohexyl, cycloheptyl,
cyclooctyl and cyclododecyl; when any of said radicals are
phenylalkyl, such groups are, for example, benzyl, phenethyl,
.alpha.-methylbenzyl and .alpha.,.alpha.-dimethylbenzyl; and when
any of said radicals is aryl, they are, for example, phenyl,
naphthyl, or when substituted by alkyl are, for example, tolyl and
xylyl. When R.sub.6 is alkyl substituted by one or more --O--
groups and/or substituted by one or more --OH, the --OR.sub.6
moiety can be --(OCH.sub.2CH.sub.2).sub.wOH or
--(OCH.sub.2CH.sub.2).sub.wOR.sub.21 where w is 1 to 12 and
R.sub.21 is alkyl of 1 to 12 carbon atoms, for example.
[0063] When E is alkylene, it is, for example, ethylene,
tetramethylene, hexamethylene, 2-methyl-1,4-tetramethylene,
hexamethylene, octamethylene, decamethylene and dodecamethylene;
when E is cycloalkylene, it is, for example, cyclopentylene,
cyclohexylene, cycloheptylene, cyclooctylene and cyclododecylene;
and when E is alkylene interrupted or terminated by cyclohexylene,
it is , for example, the saturated diyl radical derived from
limonene, herein called dihydrolimonenediyl.
[0064] A further preferred embodiment of the invention is a
compound of formula III in which R.sub.1 is tert-butyl, n is 1,
R.sub.3 is phenyl and R.sub.5 is --OR.sub.6 where R.sub.6 is a
straight chain or substituted octyl group. Yet another preferred
embodiment of the instant invention is a compound of formula C
where n is 2, R.sub.1 is tert-butyl, R.sub.3 is phenyl, and R.sub.5
is --O--R.sub.9--O-- where R.sub.9 is C.sub.2-C.sub.24alkylene
interrupted by --O-- or by
--CH.sub.2--CHOH--CH.sub.2--O--R.sub.14--O--CH.sub.2--CHOH--CH.sub.2--.
[0065] When E is alkylene, it is, for example, ethylene,
tetramethylene, hexamethylene, 2-methyl-1,4-tetramethylene,
hexamethylene, octamethylene, decamethylene and dodecamethylene;
when E is cycloalkylene, it is, for example, cyclopentylene,
cyclohexylene, cycloheptylene, cyclooctylene and cyclododecylene;
and when E is alkylene interrupted or terminated by cyclohexylene,
it is, for example, the saturated diyl radical derived from
limonene, herein called dihydrolimonenediyl.
[0066] When the instant compounds contain a free carboxyl moiety
where R.sub.2 is --CH.sub.2CH.sub.2COOR.sub.6 where R.sub.6 is
hydrogen, the alkali metal or amine salts of said acids are also
contemplated as part of this invention allowing such UV absorbers
to be used in aqueous systems due to the enhanced water solubility
of such instant compounds.
[0067] R.sub.6, R.sub.7 and R.sub.8 can be the following
C.sub.3-C.sub.18alkyl radicals which are interrupted by --O--,
--S--, or --NR.sub.11-- and can be substituted by OH: methoxyethyl,
ethoxyethyl, butoxyethyl, butoxypropyl, methylthioethyl,
CH.sub.3OCH.sub.2CH.sub.2OCH.- sub.2CH.sub.2--,
CH.sub.3CH.sub.2OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2--,
C.sub.4H.sub.9OCH.sub.2CH.sub.2OCH.sub.2CH.sub.2--,
ethylthiopropyl, octylthiopropyl, dodecyloxypropyl, 2-hydroxyethyl,
2-hydroxypropyl, 4-hydroxybutyl, 6-hydroxyhexyl,
--CH.sub.2CH.sub.2--NH--C.sub.4H.sub.9,
--CH.sub.2CH.sub.2CH.sub.2NH--C.sub.8H.sub.17 and
--CH.sub.2CH.sub.2CH.su-
b.2--N(CH.sub.3)--CH.sub.2CH(C.sub.2H.sub.5)C.sub.4H.sub.9,
[0068] R.sub.6, R.sub.7, R.sub.8, R.sub.11 and R.sub.12 can be the
following C.sub.5-C.sub.12cycloalkyl radicals: cyclopentyl,
cyclohexyl, cycloheptyl, cyclooctyl or cyclodecyl. In the case of
R.sub.6, the radical can also be substituted by --OH.
[0069] R.sub.7, R.sub.8 and R.sub.11, can be the following alkenyl
radicals: allyl, methallyl, 2-n-hexenyl or 4-n-octenyl.
[0070] When R.sub.6 is alkenyl, it can have the same meaning as
R.sub.7, R.sub.8 and R.sub.11 as alkenyl radicals, but it can also
be --CH.dbd.CH.sub.2, n-undec-10-enyl or n-octadec-9-enyl, and it
is also possible for the radical R.sub.6 to be substituted by
--OH.
[0071] R.sub.7 and R.sub.8 can be the following
C.sub.7-C.sub.15aralkyl radicals: benzyl, .alpha.-phenethyl,
2-phenethyl or 4-tert-butylbenzyl.
[0072] When R.sub.11, R.sub.13 or R.sub.12 are aralkyl, they can,
independently of one another, have the same meaning as R.sub.7 or
R.sub.8.
[0073] Independently of one another, R.sub.7, R.sub.8 and R.sub.11
can be the following C.sub.6-C.sub.14 aryl radicals: phenyl,
.alpha.-naphthyl or .beta.-naphthyl.
[0074] When R.sub.7 and R.sub.8 are C.sub.1-C.sub.3 hydroxyalkyl,
they can be the following radicals: hydroxymethyl, 2-hydroxyethyl
or 2-hydroxypropyl.
[0075] As C.sub.2-C.sub.8 alkylene, R.sub.9 and R.sub.14 can be the
following radicals: ethylene, propylene, butylene, hexylene or
octylene.
[0076] As alkylene, R.sub.10 can be the same radicals, but can, in
addition, also be higher-molecular groups such as decylene or
dodecylene.
[0077] When R.sub.9 is a C.sub.4-C.sub.8alkenylene radical, the
following is an example of a suitable group: butenylene.
[0078] In the case of R.sub.9 and R.sub.14, suitable straight or
branched chain C.sub.4-C.sub.10alkylene groups which are
interrupted by --O-- are the following groups:
--CH.sub.2CH.sub.2OCH.sub.2CH.sub.2--,
--CH(CH.sub.3)--CH.sub.2--O--CH.sub.2--CH(CH.sub.3)--CH.sub.2CH.sub.2OCH.-
sub.2CH.sub.2OCH.sub.2CH.sub.2-- and
--CH.sub.2CH.sub.2OCH.sub.2CH.sub.2OC-
H.sub.2CH.sub.2OCH.sub.2CH.sub.2--.
[0079] When R.sub.14 is a cycloalkylene radical, the following
groups are embraced: 1,3-cyclohexylene and 1,4-cyclohexylene.
[0080] When R.sub.14 is arylene, this can be, specifically, the
following groups: 1,3-phenylene or 1,4-phenylene.
[0081] As C.sub.2-C.sub.12-alkylene, Z is a straight or branched
chain. It is for example: ethylene, propylene, tetramethylene,
hexamethylene, octamethylene, dodecamethylene, 1,1-ethylidene,
2,2-propylidene, 2,2-amylidene or 2-ethylhexamethylene.
C.sub.2-C.sub.6-alkylene groups are preferred.
[0082] When Z is C.sub.4-C.sub.12-alkylene which is interrupted by
oxygen, it is for example:
--CH.sub.2--CH.sub.2--O--CH.sub.2--CH.sub.2--,
--CH.sub.2--CH.sub.2--O--CH.sub.2--CH.sub.2--CH.sub.2,
CH.sub.2--CH.sub.2--O--CH.sub.2--CH.sub.2--O--CH.sub.2--CH.sub.2 or
--CH.sub.2--CH.sub.2--O--CH.sub.2--CH.sub.2--O--CH.sub.2--CH.sub.2--O--CH-
.sub.2--CH.sub.2--, and, when alkylene is interrupted by nitrogen,
a group --N(R.sub.16)-- is meant, where R.sub.16 is as defined in
the foregoing, for example
--CH.sub.2--CH.sub.2--NH--CH.sub.2--CH.sub.2--CH.sub.2--CH.su- b.2,
--CH.sub.2--CH.sub.2--CH.sub.2--NH--(CH.sub.2).sub.8-- or
--CH.sub.2CH.sub.2--CH.sub.2--N(CH.sub.3--CH.sub.2--CH(C.sub.2H.sub.5)(CH-
.sub.2).sub.4--.
[0083] As C.sub.3-C.sub.12-alkylene substituted by a hydroxyl
group, Z is 2-hydroxytetramethylene, 2-hydroxyhexamethylene and, in
particular, 2-hydroxytrimethylene.
[0084] As cyclohexylene, Z is for example 1,4-cyclohexylene and, in
particular, 1,2-cyclohexylene.
[0085] As phenylene, Z is for example m-phenylene or
p-phenylene.
[0086] m can be zero, 1 or 2, but it is preferably 2.
[0087] p is preferably 1, but can also be zero if both X and Y are
bound by way of nitrogen.
[0088] As C.sub.1-C.sub.8-alkyl, R.sub.1 is for example: methyl,
ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl,
n-pentyl, tert-amyl, n-nexyl, n-heptyl, n-octyl, 2-ethylhexyl or
tert-octyl. Tert-butyl is preferred.
[0089] As C.sub.1-C.sub.12-alkyl, R.sub.16 R.sub.17 and R.sub.20
can have the same meaning as that given in the foregoing for
R.sub.1, and can additionally be straight or branched-chain nonyl,
decyl, undecyl, or dodecyl.
[0090] When R.sub.16 and R.sub.17 are alkyl interrupted by oxygen
atoms, the examples which apply are the same as those described in
the foregoing for Z.
[0091] Examples for R.sub.16 and R.sub.17 as aralkyl are: benzyl,
.alpha.-methylbenzyl, 1-phenylethyl, .alpha.,.alpha.-dimethylbenzyl
or 1-phenylpropyl.
[0092] If Z is ethylene, R.sub.16 and R.sub.17 together can
likewise form ethylene, which is equivalent to a bridging over by
way of a piperazine group.
[0093] When Y is a group --N(R.sub.17)--, R.sub.15 and R.sub.17
together make up a group --CO--CH.dbd.CH--CO--, and thus form the
substituent 7
[0094] on the group --X--(Z).sub.p--.
[0095] The preferred meaning of R.sub.15 is, however,
--CO--C(R.sub.18).dbd.CHR.sub.14, R.sub.18 and R.sub.19 are
preferably methyl and especially hydrogen.
[0096] R.sub.2 is --CH.sub.2--CH.sub.2--CO--O--C(G).dbd.CH.sub.2
and G is hydrogen or methyl.
[0097] The instant invention also pertains to new benzotriazoles of
formulas I, II, III or IV 8
[0098] wherein
[0099] G.sub.1 is hydrogen or halogen,
[0100] G.sub.2 is cyano, E.sub.3SO--, E.sub.3SO.sub.2--,
--COOG.sub.3, CF.sub.3--, --P(O)(C.sub.6H.sub.5).sub.2,
--CO--G.sub.3, --CO--NHG.sub.3 or --CO--N(G.sub.3).sub.2,
[0101] G.sub.3 is straight or branched chain alkyl 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 4 alkyl of 1 to 4 carbon
atoms,
[0102] E.sub.1 is hydrogen, 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,
[0103] E.sub.2 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 E.sub.2 is hydroxyl or --OE.sub.4 where E.sub.4 is
straight or branched chain alkyl of 1 to 24 carbon atoms; or said
alkyl substituted by one or more --OH, --OCO--E.sub.11, --OE.sub.4,
--NCO or --NH.sub.2 groups or mixtures thereof; or said alkyl or
said alkenyl interrupted by one or more --O--, --NH-- or
--NE.sub.4-- groups or mixtures thereof and which can be
unsubstituted or substituted by one or more --OH, --OE.sub.4 or
--NH.sub.2 groups or mixtures thereof; or E.sub.2 is --SE.sub.3,
--NHE.sub.3 or --N(E.sub.3).sub.2; or E.sub.2 is
--(CH.sub.2).sub.m--CO--X--(Z).sub.p--Y--E.sub.15
[0104] wherein
[0105] X is --O-- or --N(E.sub.16)--,
[0106] Y is --O-- or --N(E.sub.17)--,
[0107] Z is C.sub.2-C.sub.12-alkylene, C.sub.4-C.sub.12-alkylene
interrupted by one to three nitrogen atoms, oxygen atoms or a
mixture thereof, or is C.sub.3-C.sub.12-alkylene, butenylene,
butynylene, cyclohexylene or phenylene, each substituted by a
hydroxyl group,
[0108] m is zero, 1 or 2,
[0109] p is 1, or p is also zero when X and Y are --N(E.sub.16)--
and --N(E.sub.17)--, respectively,
[0110] E.sub.15 is a group --CO--C(E.sub.18).dbd.C(H)E.sub.19 or,
when Y is --N(E.sub.17)--, forms together with E.sub.17 a group
--CO--CH.dbd.CH--CO--, wherein E.sub.18 is hydrogen or methyl, and
E.sub.17 is hydrogen, methyl or --CO--X--E.sub.20, wherein E.sub.20
is hydrogen, C.sub.1-C.sub.12-alkyl or a group of the formula.
9
[0111] wherein the symbols E.sub.1, G.sub.2, X, Z, m and p have the
meanings defined above, and E.sub.16 and E.sub.17 independently of
one another are hydrogen, C.sub.1-C.sub.12-alkyl,
C.sub.3-C.sub.12-alkyl interrupted by 1 to 3 oxygen atoms, or is
cyclohexyl or C.sub.7-C.sub.15aralkyl, and E.sub.16 together with
E.sub.17 in the case where Z is ethylene, also forms ethylene,
[0112] n is 1 or 2,
[0113] when n is 1, E.sub.5 is Cl, OE.sub.6 or NE.sub.7E.sub.8,
or
[0114] E.sub.5 is --PO(OE.sub.12).sub.2, --OSi(E.sub.11).sub.3 or
--OCO--E.sub.11, or straight or branched chain
C.sub.1-C.sub.24alkyl which is interrupted by --O--, --S-- or
--NE.sub.11 and which can be unsubstituted or substituted by --OH
or --OCO--E.sub.11, C.sub.5-C.sub.12 cycloalkyl which is
unsubstituted or substituted by --OH, straight chain or branched
C.sub.2-C.sub.1.sub.8alkenyl which is unsubstituted or substituted
by --OH, C.sub.7-C.sub.15aralkyl, --CH.sub.2--CHOH--E.sub.13 or
glycidyl,
[0115] E.sub.6 is hydrogen, straight or branched chain
C.sub.1-C.sub.24alkyl which is unsubstituted or substituted by one
or more OH, OE.sub.4 or NH.sub.2 groups, or --OE.sub.6 is
--(OCH.sub.2CH.sub.2).sub.wOH or
--(OCH.sub.2CH.sub.2).sub.wOE.sub.21wher- e w is 1 to 12 and
E.sub.21 is alkyl of 1 to 12 carbon atoms,
[0116] E.sub.7 and E.sub.8 are independently hydrogen, alkyl of 1
to 18 carbon atoms, straight or branched chain
C.sub.3-C.sub.18alkyl which is interrupted by --O--, --S-- or
--NE.sub.11--, C.sub.5-C.sub.12cycloalkyl, C.sub.6-C.sub.14aryl or
C.sub.1-C.sub.3hydroxylalkyl, or E.sub.7 and E.sub.8 together with
the N atom are a pyrrolidine, piperidine, piperazine or morpholine
ring,
[0117] when n is 2, E.sub.5 is one of divalent radicals
--O--E.sub.9--O-- or --N(R.sub.11)--E.sub.10--N(E.sub.11)--,
[0118] E.sub.9 is C.sub.2-C.sub.8alkylene,
C.sub.4-C.sub.8alkenylene, C.sub.4alkynylene, cyclohexylene,
straight or branched chain C.sub.4-C.sub.10alkylene which is
interrupted by --O-- or by
--CH.sub.2--CHOH--CH.sub.2--O--E.sub.14--O--CH.sub.2--CHOH--CH.sub.2--,
[0119] E.sub.10 being straight or branched chain
C.sub.2-C.sub.12alkylene which may be interrupted by --O--,
cyclohexylene, or 10
[0120] or E.sub.10 and E.sub.11 with the two nitrogen atoms form a
piperazine ring,
[0121] E.sub.14 is straight or branched chain
C.sub.2-C.sub.8alkylene, straight or branched chain
C.sub.4-C.sub.10alkylene which is interrupted by --O--,
cycloalkylene, arylene or 11
[0122] where E.sub.7 and E.sub.8 are independently hydrogen, alkyl
of 1 to 18 carbon atoms or E.sub.7 and E.sub.8 together are
alkylene of 4 to 6 carbon atoms, 3-oxapentamethylene,
3-iminopentamethylene or 3-methyliminopentamethylene,
[0123] E.sub.11 is hydrogen, straight or branched chain
C.sub.1-C.sub.18alkyl, C.sub.5-C.sub.12cycloalkyl, straight or
branched chain C.sub.3-C.sub.8alkenyl, C.sub.6-C.sub.14aryl or
C.sub.7-C.sub.15aralkyl,
[0124] E.sub.12 is straight or branched chain
C.sub.1-C.sub.18alkyl, straight or branched chain
C.sub.3-C.sub.18alkenyl, C.sub.5-C.sub.10cycloalkyl,
C.sub.6-C.sub.16aryl or C.sub.7-C.sub.15aralkyl,
[0125] E.sub.13 is H, straight chain or branched
C.sub.1-C.sub.18alkyl which is substituted by
--PO(OR.sub.12).sub.2, phenyl which is unsubstituted or substituted
by OH, C.sub.7-C.sub.15aralkyl or --CH.sub.2OE.sub.12,
[0126] E.sub.3 is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2
to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of
5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of
6 to 10 carbon atoms or said aryl substituted by one or two alkyl
of 1 to 4 carbon atoms or 1,1,2,2-tetrahydroperfluoroalkyl where
the perfluoroalkyl moiety is of 6 to 16 carbon atoms,
[0127] L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12
carbon atoms, benzylidene, p-xylylene or cycloalkylidene, and
[0128] T is --SO--, --SO.sub.2--, --SO--E--SO--,
--SO.sub.2--E--SO.sub.2--- , --CO--, --CO--E--CO--, --COO--E--OCO--
or --CO--NG.sub.5--E--NG.sub.5--C- O--,
[0129] where E 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;
[0130] G.sub.5 is G.sub.3 or hydrogen, and
[0131] with the proviso that E.sub.1 is not phenylalkyl when
G.sub.2 is E.sub.3SO-- or E.sub.3SO.sub.2--.
[0132] Preferably, the new benzotriazole is a compound of formula
I' 12
[0133] wherein
[0134] G.sub.2 is cyano, E.sub.3SO.sub.2--, CF.sub.3--,
--COO--G.sub.3--CO--NHG.sub.3 or --CO--N(G.sub.3).sub.2,
[0135] G.sub.3 is alkyl of 1 to 12 carbon atoms,
[0136] E.sub.1 is hydrogen, phenyl, phenylalkyl of 7 to 15 carbon
atoms or said phenyl or said phenylalkyl substituted on the phenyl
ring by 1 or 2 alkyl groups of 1 to 4 carbon atoms,
[0137] E.sub.2 is alkyl of 1 to 12 carbon atoms, phenyl,
phenylalkyl of 7 to 15 carbon atoms or --CH.sub.2CH.sub.2COOG.sub.4
where G.sub.4 is hydrogen, alkyl of 1 to 24 carbon atoms or said
alkyl substituted by OH, interrupted by one to six --O-- atoms or
both substituted by OH and interrupted by one to six --O--
atoms,
[0138] E.sub.3 is alkyl of 8 to 18 carbon atom, aryl of 6 to 10
carbon atoms or said aryl substituted one or two alkyl of 1 to 4
carbon atoms, and
[0139] with the proviso that E.sub.1 is not phenylalkyl when
G.sub.2 is E.sub.3SO-- or E.sub.3SO.sub.2--.
[0140] Most preferably, in the compound of formula I',
[0141] G.sub.2 is cyano, E.sub.3SO.sub.2--, CF.sub.3--,
--CO--G.sub.3 or --CO--N(G.sub.3).sub.2,
[0142] G.sub.3 is alkyl of 1 to 8 carbon atoms,
[0143] E.sub.1 is hydrogen, phenyl or .alpha.-cumyl,
[0144] E.sub.2 is alkyl of 4 to 12 carbon atoms, and
[0145] E.sub.3 is phenyl or octyl, and with the proviso that
E.sub.1 is not .alpha.-cumyl when G.sub.2 is E.sub.3SO.sub.2--.
[0146] Especially preferred are the compounds of formula I' where
G.sub.2 is CF.sub.3--, E.sub.1 is .alpha.-cumyl, and E.sub.2 is
tert-butyl or tert-octyl.
[0147] The instant invention also pertains to a composition
stabilized against thermal, oxidative or light-induced degradation
which comprises,
[0148] (a) an organic material subject to thermal, oxidative or
light-induced degradation, and
[0149] (b) an effective stabilizing amount of a compound of formula
I, II, III or IV.
[0150] Preferably, the organic material is a natural,
semi-synthetic or synthetic polymer, especially a thermoplastic
polymer.
[0151] Most preferably, the polymer is a polyolefin or
polycarbonate, especially polyethylene or polypropylene; most
especially polypropylene.
[0152] In another preferred embodiment of the instant invention,
the organic material 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.
[0153] Most preferably, the resin is a thermoset acrylic melamine
resin or an acrylic urethane resin.
[0154] In yet another preferred embodiment of the instant
invention, the organic material is a recording material.
[0155] The recording materials according to the invention are
suitable for pressure-sensitive copying systems, photocopying
systems using microcapsules, heat-sensitive copying systems,
photographic materials and ink jet printing.
[0156] The recording materials according to the invention are
distinguished by an unexpected improvement in quality, especially
with regard to the fastness to light.
[0157] The recording materials according to the invention have the
construction known for the particular use. They consist of a
customary carrier, for example, paper or plastic film, which has
been coated with one or more layers. Depending on the type of
material, these layers contain the appropriate necessary
components, in the case of photographic materials, for example,
silver halide emulsions, dye couplers, dyes and the like. Material
particularly suitable for ink jet printing has a layer particularly
absorptive for ink on a customary carrier. Uncoated paper can also
be employed for ink jet printing. In this case the paper acts at
the same time as the carrier material and as the ink-absorbent
layer. Suitable material for ink jet printing is, for example,
described in U.S. Pat. No. 5,073,448 which is incorporated herein
by reference.
[0158] The recording material can also be transparent as, for
example, in the case of projection films.
[0159] The compounds of formula I, II, III or IV can be
incorporated into the carder material as early as the production of
the latter, in the production of paper, for example, being added to
the paper pulp. A second method of application is to spray the
carder material with an aqueous solution of compounds of formula I,
II, III or IV or to add the compounds to the coating
composition.
[0160] Coating compositions intended for transparent recording
materials suitable for projection cannot contain any particles
which scatter light, such as pigments and fillers.
[0161] The dye-binding coating composition can contain a number of
other additives, for example, antioxidants, light stabilizers
(including also UV absorbers which do not fall under the scope of
the UV absorbers of this invention), viscosity improvers,
fluorescent brighteners, biocides and/or antistatic agents.
[0162] The coating composition is usually prepared as follows: the
water-soluble components, for example, the binder, are dissolved in
water and stirred together; the solid components, for example,
fillers and other additives already described, are dispersed in
this aqueous medium; and disperison is advantageously carried out
by means of devices, for example, ultrasonic systems, turbine
stirrers, homogenizers, colloid mills, bead mills, sand mills,
high-speed stirrers and the like. The compounds of formula I, II,
III or IV can be easily incorporated into the coating
composition.
[0163] The recording material according to this invention
preferably contains 1 to 5000 mg/m.sup.2, in particular 50-1200
mg/m.sup.2, of a compound of formula I.
[0164] As already mentioned, the recording materials according to
the invention embrace a wide field. The compounds of formula I, II,
III or IV can, for example, be employed in pressure-sensitive
copying systems. They can be introduced either into the paper in
order to protect the microencapsulated dye precursors there from
light, or into the binder of the developer layer in order to
protect the dyes formed there.
[0165] Photocopying systems using light-sensitive microcapsules
which are developed by means of pressure are described in U.S. Pat.
Nos. 4,416,966; 4,483,912; 4,352,200; 4,535,050; 4,535,463;
4,551,407; 4,562,137 and 4,608,330; and also in EP-A 139,479; EP-A
162,664; EP-A 164,931; EP-A 237,024; EP-A 237,025 and EP-A 260,129.
In all these systems, the compounds can be put into the
dye-receiving layer. The compounds can, however, also be put into
the donor layer in order to protect the color formers from
light.
[0166] Photographic materials which can be stabilized are
photographic dyes and layers containing such dyes or precursors
thereof, for example, photographic paper and films. Suitable
materials are, for example, described in U.S. Pat. No. 5,364,749
which is incorporated herein by reference. The compounds of formula
I, II, III or IV act here as a UV filter against electrostatic
flashes. In color photographic materials, couplers and dyes are
also protected against photochemical decomposition.
[0167] The instant compounds can be used for all types of color
photographic materials. For example, they can be employed for color
paper, color reversal paper, direct-positive color material, color
negative film, color positive film, color reversal film and the
like. They are preferably used inter alia for photographic color
material which contains a reversal substrate or form positives.
[0168] Color-photographic recording materials usually contain, on a
support, a blue-sensitive and/or a green-sensitive and/or a
red-sensitive silver halide emulsion layer and, if desired, a
protection layer, with the instant compounds being, preferably,
either in the green-sensitive or the red-sensitive layer or in a
layer between the green-sensitive and the red-sensitive layer or in
a layer on top of the silver halide emulsion layers.
[0169] The compounds of formula I, II, III or IV can also be
employed in recording materials based on the principles of
photopolymerization, photoplasticization or the rupture of
microcapsules, or in cases where heat-sensitive and light-sensitive
diazonium salts, leuko dyes having an oxidizing agent or dye
lactones having Lewis acids are used.
[0170] Furthermore, the instant compounds can be employed in
recording materials for dye diffusion transfer printing, thermal
wax transfer printing and non-matrix printing and for use with
electrostatic, electrographic, electrophoretic, magnetographic and
laser-electrophotographic printers and pen-plotters. Of the above,
recording materials for dye diffusion transfer printing are
preferred, for example, as described in EP-A 507,734.
[0171] The instant compounds can also be employed in inks,
preferably for ink jet printing, for example, as described in U.S.
Pat. No. 5,098,477 which is incorporated herein by reference.
[0172] The compounds of this invention exhibit superior hydrolytic
stability, handling and storage stability as well as good
resistance to extractability when present in a stabilized
composition.
[0173] The methodology to make the instant compounds is described
in the prior art. The intermediates needed to make the instant
compounds are largely items of commerce.
[0174] Preferred compounds are those in which one of X and Y is
--O--; and particularly those in which both X and Y are --O--.
[0175] In general polymers which can be stabilized include
[0176] 1. Polymers of monoolefins and diolefins, for example
polypropylene, polyisobutylene, polybut-1-ene,
poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as
polymers of cycloolefins, for instance of cyclopentene or
norbornene, polyethylene (which optionally can be crosslinked), for
example high density polyethylene (HDPE), low density polyethylene
(LDPE), linear low density polyethylene (LLDPE), branched low
density polyethylene (BLDPE).
[0177] Polyolefins, i.e. the polymers of monoolefins exemplified in
the preceding paragraph, preferably polyethylene and polypropylene,
can be prepared by different, and especially by the following,
methods:
[0178] a) radical polymerisation (normally under high pressure and
at elevated temperature).
[0179] b) catalytic polymerisation using a catalyst that normally
contains one or more than one metal of groups IVb, Vb, VIb or VIII
of the Periodic Table. These metals usually have one or more than
one ligand, typically oxides, halides, alcoholates, esters, ethers,
amines, alkyls, alkenyls and/or aryls that may be either .pi.- or
.sigma.-coordinated. These metal complexes may be in the free form
or fixed on substrates, typically on activated magnesium chloride,
titanium(III) chloride, alumina or silicon oxide. These catalysts
may be soluble or insoluble in the polymerisation medium. The
catalysts can be used by themselves in the polymerisation or
further activators may be used, typically metal alkyls, metal
hydrides, metal alkyl halides, metal alkyl oxides or metal
alkyloxanes, said metals being elements of groups Ia, Ia and/or
IIIa of the Periodic Table. The activators may be modified
conveniently with further ester, ether, amine or silyl ether
groups. These catalyst systems are usually termed Phillips,
Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene
or single site catalysts (SSC).
[0180] 2. Mixtures of the polymers mentioned under 1), for example
mixtures of polypropylene with polyisobutylene, polypropylene with
polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of
different types of polyethylene (for example LDPE/HDPE).
[0181] 3. Copolymers of monoolefins and diolefins with each other
or with other vinyl monomers, for example ethylene/propylene
copolymers, linear low density polyethylene (LLDPE) and mixtures
thereof with low density polyethylene (LDPE), propylene/but-1-ene
copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene
copolymers, ethylene/hexene copolymers, ethylene/methylpentene
copolymers, ethylene/heptene copolymers, ethylene/octene
copolymers, propylene/butadiene copolymers, isobutylene/isoprene
copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl
methacrylate copolymers, ethylene/vinyl acetate copolymers and
their copolymers with carbon monoxide or ethylene/acrylic acid
copolymers and their salts (ionomers) as well as terpolymers of
ethylene with propylene and a diene such as hexadiene,
dicyclopentadiene or ethylidene-norbornene; and mixtures of such
copolymers with one another and with polymers mentioned in 1)
above, for example polypropylene/ethylene-propylene copolymers,
LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic
acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or
random polyalkylene/carbon monoxide copolymers and mixtures thereof
with other polymers, for example polyamides.
[0182] 4. Hydrocarbon resins (for example C.sub.5-C.sub.9)
including hydrogenated modifications thereof (e.g. tackifiers) and
mixtures of polyalkylenes and starch.
[0183] 5. Polystyrene, poly(p-methylstyrene),
poly(.alpha.-methylstyrene).
[0184] 6. Copolymers of styrene or .alpha.-methylstyrene with
dienes or acrylic derivatives, for example styrene/butadiene,
styrene/acrylonitrile, styrene/alkyl methacrylate,
styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl
methacrylate, styrene/maleic anhydride,
styrene/acrylonitrile/methyl acrylate; mixtures of high impact
strength of styrene copolymers and another polymer, for example a
polyacrylate, a diene polymer or an ethylene/propylene/diene
terpolymer, and block copolymers of styrene such as
styrene/butadiene/styrene, styrene/isoprene/styrene,
styrene/ethylene/butylene/styrene or
styrene/ethylene/propylene/styrene.
[0185] 7. Graft copolymers of styrene or .alpha.-methylstyrene, for
example styrene on polybutadiene, styrene on polybutadiene-styrene
or polybutadiene-acrylonitrile copolymers; styrene and
acrylonitrile (or methacrylonitrile) on polybutadiene; styrene,
acrylonitrile and methyl methacrylate on polybutadiene; styrene and
maleic anhydride on polybutadiene; styrene, acrylonitrile and
maleic anhydride or maleimide on polybutadiene; styrene and
maleimide on polybutadiene; styrene and alkyl acrylates or
methacrylates on polybutadiene; styrene and acrylonitrile on
ethylene/propylene/diene terpolymers; styrene and acrylonitrile on
polyalkyl acrylates or polyalkyl methacrylates, styrene and
acrylonitrile on acrylate/butadiene copolymers, as well as mixtures
thereof with the copolymers listed under 6), for example the
copolymer mixtures known as ABS, MBS, ASA or AES polymers.
[0186] 8. Halogen-containing polymers such as polychloroprene,
chlorinated rubbers, chlorinated or sulfochlorinated polyethylene,
copolymers of ethylene and chlorinated ethylene, epi-chlorohydrin
homo- and copolymers, especially polymers of halogen-containing
vinyl compounds, for example polyvinyl chloride, polyvinylidene
chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as
copolymers thereof such as vinyl chloride/vinylidene chloride,
vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate
copolymers.
[0187] 9. Polymers derived from .alpha.,.beta.-unsaturated acids
and derivatives thereof such as polyacrylates and
polymethacrylates; polymethyl methacrylates, polyacrylamides and
polyacrylonitriles, impact-modified with butyl acrylate.
[0188] 10. Copolymers of the monomers mentioned under 9) with each
other or with other unsaturated monomers, for example
acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl acrylate
copolymers, acrylonitrile/alkoxyalkyl acrylate or
acrylonitrile/vinyl halide copolymers or acrylonitrile/ alkyl
methacrylate/butadiene terpolymers.
[0189] 11. Polymers derived from unsaturated alcohols and amines or
the acyl derivatives or acetals thereof, for example polyvinyl
alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate,
polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or
polyallyl melamine; as well as their copolymers with olefins
mentioned in 1) above.
[0190] 12. Homopolymers and copolymers of cyclic ethers such as
polyalkylene glycols, polyethylene oxide, polypropylene oxide or
copolymers thereof with bisglycidyl ethers.
[0191] 13. Polyacetals such as polyoxymethylene and those
polyoxymethylenes which contain ethylene oxide as a comonomer;
polyacetals modified with thermoplastic polyurethanes, acrylates or
MBS.
[0192] 14. Polyphenylene oxides and sulfides, and mixtures of
polyphenylene oxides with styrene polymers or polyamides.
[0193] 15. Polyurethanes derived from hydroxyl-terminated
polyethers, polyesters or polybutadienes on the one hand and
aliphatic or aromatic polyisocyanates on the other, as well as
precursors thereof.
[0194] 16. Polyamides and copolyamides derived from diamines and
dicarboxylic acids and/or from aminocarboxylic acids or the
corresponding lactams, for example polyamide 4, polyamide 6,
polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide
12, aromatic polyamides starting from m-xylene diamine and adipic
acid; polyamides prepared from hexamethylenediamine and isophthalic
or/and terephthalic acid and with or without an elastomer as
modifier, for example poly-2,4,4,-trimethylhexame- thylene
terephthalamide or poly-m-phenylene isophthalamide; and also block
copolymers of the aforementioned polyamides with polyolefins,
olefin copolymers, ionomers or chemically bonded or grafted
elastomers; or with polyethers, e.g. with polyethylene glycol,
polypropylene glycol or polytetramethylene glycol; as well as
polyamides or copolyamides modified with EPDM or ABS; and
polyamides condensed during processing (RIM polyamide systems).
[0195] 17. Polyureas, polyimides, polyamide-imides and
polybenzimidazoles.
[0196] 18. Polyesters derived from dicarboxylic acids and diols
and/or from hydroxycarboxylic acids or the corresponding lactones,
for example polyethylene terephthalate, polybutylene terephthalate,
poly-1,4-dimethylolcyclohexane terephthalate and
polyhydroxybenzoates, as well as block copolyether esters derived
from hydroxyl-terminated polyethers; and also polyesters modified
with polycarbonates or MBS.
[0197] 19.- Polycarbonates and polyester carbonates.
[0198] 20. Polysulfones, polyether sulfones and polyether
ketones.
[0199] 21. Crosslinked polymers derived from aldehydes on the one
hand and phenols, ureas and melamines on the other hand, such as
phenol/formaldehyde resins, urea/formaldehyde resins and
melamine/formaldehyde resins.
[0200] 22. Drying and non-drying alkyd resins.
[0201] 23. Unsaturated polyester resins derived from copolyesters
of saturated and unsaturated dicarboxylic acids with polyhydric
alcohols and vinyl compounds as crosslinking agents, and also
halogen-containing modifications thereof of low flammability.
[0202] 24. Crosslinkable acrylic resins derived from substituted
acrylates, for example epoxy acrylates, urethane acrylates or
polyester acrylates.
[0203] 25. Alkyd resins, polyester resins and acrylate resins
crosslinked with melamine resins, urea resins, polyisocyanates or
epoxy resins.
[0204] 26. Crosslinked epoxy resins derived from polyepoxides, for
example from bisglycidyl ethers or from cycloaliphatic
diepoxides.
[0205] 27. Natural polymers such as cellulose, rubber, gelatin and
chemically modified homologous derivatives thereof, for example
cellulose acetates, cellulose propionates and cellulose butyrates,
or the cellulose ethers such as methyl cellulose; as well as rosins
and their derivatives.
[0206] 28. Blends of the aforementioned polymers (polyblends), for
example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS,
PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates,
POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS,
PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO.
[0207] 29. Naturally occurring and synthetic organic materials
which are pure monomeric compounds or mixtures of such compounds,
for example mineral oils, animal and vegetable fats, oil and waxes,
or oils, fats and waxes based on synthetic esters (e.g. phthalates,
adipates, phosphates or trimellitates) and also mixtures of
synthetic esters with mineral oils in any weight ratios, typically
those used as spinning compositions, as well as aqueous emulsions
of such materials.
[0208] 30. Aqueous emulsions of natural or synthetic rubber, e.g.
natural latex or latices of carboxylated styrene/butadiene
copolymers.
[0209] 31. Polysiloxanes such as the soft, hydrophilic
polysiloxanes described, for example, in U.S. Pat. No. 4,259,467;
and the hard polyorganosiloxanes described, for example, in U.S.
Pat. No. 4,355,147.
[0210] 32. Polyketimines in combination with unsaturated acrylic
polyacetoacetate resins or with unsaturated acrylic resins. The
unsaturated acrylic resins include the urethane acrylates,
polyether acrylates, vinyl or acryl copolymers with pendant
unsaturated groups and the acrylated melamines. The polyketimines
are prepared from polyamines and ketones in the presence of an acid
catalyst.
[0211] 33. Radiation curable compositions containing ethylenically
unsaturated monomers or oligomers and a polyunsaturated aliphatic
oligomer.
[0212] 34. Epoxymelamine resins such as light-stable epoxy resins
crosslinked by an epoxy functional coetherified high solids
melamine resin such as LSE-4103 (Monsanto).
[0213] In general, the compounds of the present invention are
employed in from about 0.01 to about 5% by weight of the stabilized
composition, although this will vary with the particular substrate
and application. An advantageous range is from about 0.05 to about
3%, and especially 0.05 to about 1%.
[0214] The stabilizers of the instant invention may readily be
incorporated into the organic polymers by conventional techniques,
at any convenient stage prior to the manufacture of shaped articles
therefrom. For example, the stabilizer may be mixed with the
polymer in dry powder form, or a suspension or emulsion of the
stabilizer may be mixed with a solution, suspension, or emulsion of
the polymer. The resulting stabilized polymer compositions of the
invention may optionally also contain from about 0.01 to about 5%,
preferably from about 0.025 to about 2%, and especially from about
0.1 to about 1% by weight of various conventional additives, such
as the materials listed below, or mixtures thereof.
[0215] 1. Antioxidants
[0216] 1.1. Alkylated monophenols, for example,
[0217]
[0218] 2,6-di-tert-butyl-4-methylphenol
[0219] 2-tert-butyl-4,6-dimethylphenol
[0220] 2,6-di-tert-butyl-4-ethylphenol
[0221] 2,6-di-tert-butyl-4-n-butylphenol
[0222] 2,6-di-tert-butyl-4-i-butylphenol
[0223] 2,6-di-cyclopentyl-4-methylphenol
[0224] 2-(.alpha.-methylcyclohexyl)-4,6-dimethylphenol
[0225] 2,6-di-octadecyl-4-methylphenol
[0226] 2,4,6-tri-cyclohexylphenol
[0227] 2,6-di-tert-butyl-4-methoxymethylphenol
[0228]
[0229] 1.2. Alkylated hydroquinones, for example,
[0230]
[0231] 2,6-di-tert-butyl-4-methoxyphenol
[0232] 2,5-di-tert-butyl-hydroquinone
[0233] 2,5-di-tert-amyl-hydroquinone
[0234] 2,6-diphenyl-4-octadecyloxyphenol
[0235]
[0236] 1.3. Hydroxylated thiodiphenyl ethers, for example,
[0237]
[0238] 2,2'-thio-bis-(6-tert-butyl-4-methylphenol)
[0239] 2,2'-thio-bis-(4-octylphenol)
[0240] 4,4'-thio-bis-(6-tert-butyl-3-methylphenol)
[0241] 4,4'thio-bis-(6-tert-butyl-2-methylphenol)
[0242]
[0243] 1.4. Alkylidene-bisphenols, for example,
[0244]
[0245] 2,2'-methylene-bis-(6-tert-butyl-4-methylphenol)
[0246] 2,2'-methylene-bis-(6-tert-butyl-4-ethylphenol)
[0247]
2,2'-methylene-bis-[4-methyl-6-(.alpha.-methylcyclohexyl)-phenol]
[0248] 2,2'-methylene-bis-(4-methyl-6-cyclohexylphenol)
[0249] 2,2'-methylene-bis-(6-nonyl-4-methylphenol)
[0250]
2,2'-methylene-bis-[6-(.alpha.-methylbenzyl)-4-nonylphenol]
[0251]
2,2'-methylene-bis-[6-(.alpha.,.alpha.-dimethylbenzyl)-4-nonylpheno-
l]
[0252] 2,2'-methylene-bis-(4,6-di-tert-butylphenol)
[0253] 2,2'-ethylidene-bis-(4,6-di-tert-butylphenol)
[0254] 2,2'-ethylidene-bis-(6-tert-butyl-4-isobutylphenol)
[0255] 4,4'-methylene-bis-(2,6-di-tert-butylphenol)
[0256] 4,4'-methylene-bis-(6-tert-butyl-2-methylphenol)
[0257] 1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane
[0258]
2,6-di-(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol
[0259]
1,1,3-tris-(5-tert-butyl-4-hydroxy-2-methylphenyl)-butane
[0260]
1,1-bis-(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercapto-
butane
[0261] ethyleneglycol
bis-[3,3-bis-(3'-tert-butyl-4'-hydroxyphenyl)-butyra- te]
[0262]
di-(3-tert-butyl-4-hydroxy-5-methylphenyl)-dicyclopentadiene
[0263]
di-[2-(3'-tert-butyl-2'-hydroxy-5'-methyl-benzyl)-6-tert-butyl-4-me-
thylphenyl]terephthalate.
[0264]
[0265] 1.5. Benzyl compounds, for example,
[0266]
[0267]
1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzen-
e
[0268] di-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide
[0269] 3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid
isooctyl ester
[0270] bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol
terephthalate
[0271] 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)
isocyanurate
[0272] 1,3,5-tris-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)
isocyanurate
[0273] 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid
dioctadecyl ester
[0274] 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl
ester, calcium-salt
[0275]
[0276] 1.6. Acylaminophenols, for example,
[0277]
[0278] 4-hydroxy-lauric acid anilide
[0279] 4-hydroxy-stearic acid anilide
[0280]
2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazin-
e
[0281] octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate
[0282]
[0283] 1.7. Esters of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid with
monohydric or polyhydric alcohols, for example,
1 methanol diethylene glycol octadecanol triethylene glycol
1,6-hexanediol pentaerythritol neopentyl glycol tris-hydroxyethyl
isocyanurate thiodiethylene glycol di-hydroxyethyl oxalic acid
diamide triethanolamine triisopropanolamine
[0284] 1.8. Esters of
.beta.-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propi- onic acid
with monohydric or polyhydric alcohols, for example,
2 methanol diethylene glycol octadecanol triethylene glycol
1,6-hexanediol pentaerythritol neopentyl glycol tris-hydroxyethyl
isocyanurate thiodiethylene glycol di-hydroxyethyl oxalic acid
diamide triethanolamine triisopropanolamine
[0285] 1.9. Amides of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid for
example,
[0286]
[0287] N,N
'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexamethylene-
diamine
[0288]
N,N'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-trimethylenedi-
amine
[0289]
N,N-'-di-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine
[0290]
[0291] 1.10 Diarylamines, for example,
[0292] diphenylamine, N-phenyl-1-naphthylamine,
N-(4-tert-octylphenyl)-1-n- aphthylamine,
4,4'-di-tert-octyl-diphenylamine, reaction product of
N-phenylbenzylamine and 2,4,4-trimethylpentene, reaction product of
diphenylamine and 2,4,4-trimethylpentene, reaction product of
N-phenyl-1-naphthylamine and 2,4,4-trimethylpentene.
[0293]
[0294] 2. UV absorbers and light stabilizers
[0295]
[0296] 2.1. 2-(2'-Hydroxyphenyl)-benzotriazoles, for example, the
5'-methyl-, 3',5'-di-tert-butyl-, 5'-tert-butyl-,
5'-(1,1,3,3-tetramethyl- butyl)-5-chloro-3',5'-di-tert-butyl-,
5-chloro-3'-tert-butyl-5'-methyl-, 3'-sec-butyl-5'-tert-butyl-,
4'-octoxy, 3',5'-di-tert-amyl-,
3',5'-bis-(.alpha.,.alpha.-dimethylbenzyl),
3'-tert-butyl-5'-(2-(omega-hy-
droxy-octa-(ethyleneoxy)carbonyl-ethyl)-, 3'-dodecyl-5'-methyl-,
and 3'-tert-butyl-5'-(2-octyloxycarbonyl)ethyl-, and
dodecylated-5'-methyl derivatives.
[0297] 2.2. 2-Hydroxy-benzophenones, for example, the 4-hydroxy-,
4-methoxy-, 4-octoxy, 4-decyloxy-, 4-dodecyloxy-, 4-benzyloxy,
4,2',4'-trihydroxy- and 2'-hydroxy-4,4'-dimethoxy derivatives.
[0298] 2.3. Esters of optionally substituted benzoic acids for
example, phenyl salicylate, 4-tert-butylphenyl salicylate,
octylphenyl salicylate, dibenzoylresorcinol,
bis-(4-tert-butylbenzoyl)-resorcinol, benzoylresorcinol,
3,5-di-tert-butyl-4-hydroxybenzoic acid 2,4-di-tert-butylphenyl
ester and 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl
ester.
[0299] 2.4. Acrylates, for example,
(.alpha.-cyano-.beta.,.beta.-diphenyla- crylic acid ethyl ester or
isooctyl ester, .alpha.-carbomethoxy-cinnamic acid methyl ester,
.alpha.-cyano-.beta.-methyl-p-methoxy-cinnamic acid methyl ester or
butyl ester, .alpha.-carbomethoxy-p-methoxy-cinnamic acid methyl
ester, N-(.beta.-carbomethoxy-5-cyanovinyl)-2-methyl-indoline.
[0300] 2.5. Nickel compounds, for example, nickel complexes of
2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)-phenol], such as the
1:1 or 1:2 complex, optionally with additional ligands such as
n-butylamine, triethanolamine or N-cyclohexyl-diethanolamine,
nickel dibutyldithiocarbamate, nickel salts of
4-hydroxy-3,5-di-tert-butylbenzyl- phosphonic acid monoalkyl
esters, such as of the methyl, ethyl or butyl ester, nickel
complexes of ketoximes such as of 2-hydroxy-4-methyl-phenyl undecyl
ketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazo-
le, optionally with additional ligands.
[0301] 2.6. Sterically hindered amines, for example
bis-(2,2,6,6-tetramethylpiperidyl) sebacate,
bis-(1,2,2,6,6-pentamethylpi- peridyl) sebacate,
n-butyl-3,5-di-tert.butyl-4-hydroxybenzyl malonic acid
bis-(1,2,2,6,6-pentanemethylpiperidyl)ester, condensation product
of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and
succinic acid, condensation product of
N,N'-(2,2,6,6-tetra-methylpiperidyl)-hexamethylen- ediamine and
4-tert-octylamino-2,6-dichloro-s-triazine,
tris-(2,2,6,6-tetramethylpiperidyl)-nitrilotriacetate,
tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)
1,2,3,4-butanetetracarboxylate- ,
1,1'(1,2-ethanediyl)-bis-(3,3,5,5-tetramethylpiperazinone),
bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.
[0302] 2.7. Oxalic acid diamides, for example,
4,4'-di-octyloxy-oxanilide,
2,2'-di-octyloxy-5,5'-di-tert-butyl-oxanilide,
2,2'-di-dodecyloxy-5,5'-di- -tert-butyl-oxanilide,
2-ethoxy-2'-ethyl-oxanilide, N,N'-bis
(3-dimethylaminopropyl)-oxalamide,
2-ethoxy-5-tert-butyl-2'-ethyloxanilid- e and its mixture with
2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxanilide and mixtures of
ortho- and para-methoxy- as well as of o- and
p-ethoxy-disubstituted oxanilides.
[0303] 2.8. Hydroxyphenyl-s-triazines, for example
2,6-bis-(2,4-dimethylph-
enyl)-4-(2-hydroxy-4-octyloxyphenyl)-s-triazine;
2,6-bis-(2,4-dimethylphen- yl)-4-(2,4-dihydroxyphenyl)-s-triazine;
2,4-bis(2,4-dihydroxyphenyl)-6-(4-- chlorophenyl)-s-triazine;
2,4-bis[2-hydroxy-4-(2-hydroxy-ethoxy)phenyl]
-6-(4-chlorophenyl)-s-triazine;
2,4-bis[2-hydroxy-4-(2-hydroxy-4-(2-hydro- xy-ethoxy)phenyl]
-6-(2,4-dimethylphenyl)-s-triazine;
2,4-bis[2-hydroxy-4-(2-hydroxyethoxy)-phenyl]
-6-(4-bromophenyl)-s-triazi- ne;
2,4-bis[2-hydroxy-4-(2-acetoxyethoxy)phenyl]-6-(4-chloro-phenyl)-s-tri-
azine,
2,4-bis(2,4-dihydroxyphenyl)-6-(2,4-dimethylphenyl)-s-triazine.
[0304] 3. Metal deactivators, for example, N,N'-diphenyloxalic acid
diamide, N-salicylal-N'-salicyloyl-hydrazine,
N,N'-bis-salicyloylhydrazin- e,
N,N'-bis-(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazine,
3-salicyloylamino-1,2,4-triazole, bis-benzylidene-oxalic acid
dihydrazide.
[0305] 4. Phosphites and phosphonites, for example, triphenyl
phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites,
tri-(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl
phosphite, di-stearyl-pentaerythritol diphosphite,
tris-(2,4-di-tert-butylphenyl) phosphite,
di-isodecyl-pentaerythritol diphosphite,
di-(2,4,6-tri-tert-butylphenyl)-pentaerythritol diphosphite,
di-(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite,
di-(2,4-di-tert-butylphenyl)pentaerythritol diphosphite,
tristearyl-sorbitol triphosphite,
tetrakis-(2,4-di-tert-butylphenyl)
4,4'-diphenylylenediphosphonite.
[0306] 5. Compounds which destroy peroxide, for example, esters of
.beta.-thiodipropionic acid, for example the lauryl, stearyl,
myristyl or tridecyl esters, mercapto-benzimidazole or the zinc
salt of 2-mercaptobenzimidazole, zinc dibutyl-dithiocarbamate,
dioctadecyl disulfide, pentaerythritol
tetrakis-(.beta.-dodecylmercapto)-propionate.
[0307] 6. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,
N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,
N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,
N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,
N-hexadecyl-N-octadecyl-hydroxylamine,
N-heptadecyl-N-octadecylhydroxylam- ine, N,N-dialkylhydroxylamine
derived from hydrogenated tallow amine.
[0308] 7. Nitrones, for example, N-benzyl-alpha-phenyl nitrone,
N-ethyl-alpha-methyl nitrone, N-octyl-alpha-heptyl nitrone,
N-lauryl-alpha-undecyl nitrone, N-tetradecyl-alpha-tridecyl
nitrone, N-hexadecyl-alpha-pentadecyl nitrone,
N-octadecyl-alpha-heptadecylnitrone- , N-hexadecyl-alpha-heptadecyl
nitrone, N-octadecyl-alpha-pentadecyl nitrone,
N-heptadecyl-alpha-heptadecyl nitrone, N-octadecyl-alpha-hexadec-
yl nitrone, nitrone derived from N,N-dialkylhydroxylamine derived
from hydrogenated tallow amine.
[0309] 8. Polyamide stabilizers, for example copper salts in
combination with iodides and/or phosphorus compounds and salts of
divalent manganese.
[0310] 9. Basic co-stabilizers, for example, melamine,
polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea
derivatives, hydrazine derivatives, amines, polyamides,
polyurethanes, alkali metal salts and alkaline earth metal salts of
higher fatty acids for example Ca stearate, Zn stearate, Mg
stearate, Na ricinoleate and K palmitate, antimony pyrocatecholate
or zinc pyrocatecholate.
[0311] 10. Nucleating agents, for example, 4-tert-butyl-benzoic
acid, adipic acid, diphenylacetic acid.
[0312] 11. Fillers and reinforcing agents, for example, calcium
carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica,
barium sulfate, metal oxides and hydroxides, carbon black,
graphite.
[0313] 12. Other additives, for example, plasticizers, lubricants,
emulsifiers, pigments, optical brighteners, flameproofing agents,
anti-static agents, blowing agents and thiosynergists such as
dilauryl thiodipropionate or distearyl thiodipropionate.
[0314] 13. Benzofuranones and indolinones, for example those
disclosed in U.S. Pat. No. 4,325,863, U.S. Pat. No. 4,338,244 or
U.S. Pat. No. 5,175,312, or
3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butyl-benzo-furan-
-2-one,
5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-on-
e,
3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-on-
e], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)-benzofuran- 2-one,
3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,
3-(3,5-di-methyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.
[0315] The co-stabilizers, with the exception of the benzofuranones
listed under 11, are added for example in concentrations of 0.01 to
10%, relative to the total weight of the material to be
stabilized.
[0316] Further preferred compositions comprise, in addition to
components (a) and (b) further additives, in particular phenolic
antioxidants, light stabilizers or processing stabilizers.
[0317] Particularly preferred additives are phenolic antioxidants
(item I of the list), sterically hindered amines (item 2.6 of the
list), phosphites and phosphonites (item 4 of the list) and
peroxide-destroying compounds (item 5.) of the list.
[0318] Additional additives (stabilizers) which are also
particularly preferred are benzofuran-2-ones, such as described,
for example, in U.S. Pat. No. 4,325,863, U.S. Pat. No. 4,338,244 or
U.S. Pat. No. 5,175,312.
[0319] The phenolic antioxidant of particular interest is selected
from the group consisting of n-octadecyl
3,5-di-tert-butyl-4-hydroxyhydrocinna- mate, neopentanetetrayl
tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate- ),
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-tri-
s(3,5-di-tert-butyl-4-hydroxy-benzyl)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]isocyanu-
rate, 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-hy-
droxyanilino)-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-hydroxybenzylphosphonate), ethylene
bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl
3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate,
bis(3,5di-tert-butyl-4-- hydroxyhydrocinnamoyl)hydrazide, and N,N
'-bis [2- (3,5-di-tert-butyl-4-hy-
droxyhydrocinnamoyloxy)-ethyl]-oxamide.
[0320] A most preferred phenolic antioxidant is neopentanetetrayl
tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl
3,5-di-tert-butyl-4-hydroxyhydrocinnamate,
1,3,5-tri-methyl-2,4,6-tris(3,-
5-di-tert-butyl-4-hydroxybenzyl)benzene,
1,3,5-tris(3,5-di-tert-butyl-4-hy- droxybenzyl)isocyanurate,
2,6-di-tert-butyl-p-cresol or
2,2'-ethylidene-bis(4,6-di-tert-butylphenol).
[0321] The hindered amine compound of particular interest 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-hydroxybenzy- l)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-tetramethylpiperidi- n-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]henei-
cosane, polycondensation product of
2,4-dichloro-6-tert-octylamino-s-triaz- ine and
4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine),
polycondensation product of
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydr- oxypiperidine and
succinic acid, polycondensation product of
4,4'-hexamethylenebis-(amino-2,2,6,6-tetra-methylpiperidine) 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--
pentamethyl-piperidin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazade-
cane, 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-pentamethylpiper-
idin-4-yl/.beta.,.beta.,.beta.',.beta.'-tetramethyl-3,9-(2,4,8,10-tetraoxa-
spiro[5.5]-undecane)diethyl] 1,2,3,4-butanetetracarboxylate,
octamethylene bis(2,2,6,6-tetramethyl-piperidin-4-carboxylate),
4,4'-ethylenebis(2,2,6,- 6-tetramethylpiperazin-3-one),
N-2,2,6,6-tetramethyl-piperidin-4-yl-n-dode- cylsuccinimide,
N-1,2,2,6,6-pentamethyl-piperidin-4-yl-n-dodecylsuccinimid- e,
N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yln-dodecylsuccinimide,
1-acetyl3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-di-
one, di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,
di-(1-cyclohexyloxy-2,2,6,6-tetra-methylpiperidin-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.
[0322] A most preferred hindered amine compound is
bis(2,2,6,6-tetramethyl- piperidin-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-hy-
droxybenzyl)butylmalonate, the polycondensation product of
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and
succinic acid, the polycondensation product of
2,4-dichloro-6-tert-octylamino-s-tr- iazine 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-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.
[0323] The instant composition can additionally contain another UV
absorber selected from the group consisting of the s-triazines, the
oxanilides, the hydroxybenzophenones, benzoates and the
.alpha.-cyanoacrylates.
[0324] Particularly, the instant composition may additionally
contain an effective stabilizing amount of at least one other
2-hydroxyphenyl-2H-benzotriazole; another tris-aryl-s-triazine; or
hindered amine or mixtures thereof.
[0325] Preferably, the 2-hydroxyphenyl-2H-benzotriazole is selected
from the group consisting of
[0326]
[0327] 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;
[0328]
2-[2-hydroxy-3,5-di(.alpha.,.alpha.-dimethylbenzyl)phenyl]-2H-benzo-
triazole;
[0329]
2-[2-hydroxy-3-(.alpha.,.alpha.-dimethylbenzyl)-5-octylphenyl]-2H-b-
enzotriazole;
[0330]
2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carb-
onyl)ethyl]-phenyl}-2H-benzotriazole; and
[0331]
2-{(2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-
-benzo-triazole.
[0332] Preferably, the other tris-aryl-s-triazine is selected from
the group consisting of
[0333]
[0334]
2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazi-
ne;
[0335] 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine;
[0336]
2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-do-/tri-decyloxy-2-hy-
droxypropoxy)-phenyl]-s-triazine; and
[0337] 2-(2-hydroxyethylamino)-4,6-bis
[N-butyl-N-(1-cyclohexyloxy-2,2,6,6-
-tetramethyl-piperidin-4-yl)amino]-s-triazine.
[0338] The alkyd resin lacquers which can be stabilized against the
action of light and moisture in accordance with the instant
invention are the conventional stoving lacquers which are used in
particular for coating automobiles (automobile finishing lacquers),
for example lacquers based on alkyd/melamine resins and
alkyd/acrylic/melamine resins (see H. Wagner and H. F. Sarx,
"Lackkunstharze" (1977), pages 99-123). Other crosslinking agents
include glycouril resins, blocked isocyanates or epoxy resins.
[0339] The lacquers stabilized in accordance with the invention are
suitable both for metal finish coatings and solid shade finishes,
especially in the case of retouching finishes, as well as various
coil coating applications. The lacquers stabilized in accordance
with the invention are preferably applied in the conventional
manner by two methods, either by the single-coat method or by the
two-coat method. In the latter method, the pigment-containing base
coat is applied first and then a covering coat of clear lacquer
over it.
[0340] It is also to be noted that the compounds of the present
invention are applicable for use in non-acid catalyzed thermoset
resins such as epoxy, epoxy-polyester, vinyl, alkyd, acrylic and
polyester resins, optionally modified with silicon, isocyanates or
iso-cyanurates. The epoxy and epoxy-polyester resins are
crosslinked with conventional cross-linkers such as acids, acid
anhydrides, amines and the like. Correspondingly, the epoxide may
be utilized as the crosslinking agent for various acrylic or
polyester resin systems that have been modified by the presence of
reactive groups on the backbone structure.
[0341] When used in two-coat finishes, the compounds of the instant
invention can be incorporated in the clear coat or both in the
clear coat and in the pigmented base coat.
[0342] When water-soluble, water miscible or water dispersible
coating are desired ammonium salts of acid groups present in the
resin are formed. Powder coating composition can be prepared by
reacting glycidyl methacrylate with selected alcohol
components.
[0343] The instant benzotriazoles are made by conventional methods
for preparing such compounds. The usual procedure involves the
diazotization of a substituted o-nitroaniline followed by coupling
the resultant diazonium salt with a substituted phenol and
reduction of the azobenzene intermediate to the corresponding
desired benzotriazole. The starting materials for these
benzotriazoles are largely items of commerce or can be prepared by
normal methods of organic synthesis.
[0344] While the instant benzotriazoles with their enhanced
durability are particularly suited for automotive coating
applications, it is contemplated that they will also be espeically
useful in other applications where their enhanced durability is
required such as in solar films and the like.
[0345] The following examples are for illustrative purposes only
and are not to be construed to limit the scope of the instant
invention in any manner whatsoever.
EXAMPLE 1
5-Trifluoromethyl-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benz-
otriazole
[0346] a. Diazotization of 4-amino-3-nitro-benzotrifluoride
[0347] To a 500 ml 3-necked flask, equipped with a mechanical
stirrer, are added 41.2 g of 4-amino-3-nitro-benzotrifluoride, 52
ml of concentrated hydrochloride acid and 100 ml of distilled
water. The stirred solution is cooled to 5.degree. C. and 17.3 g of
sodium nitrite dissolved in 50 ml of water are added. The solution
is stirred at 0 to 5.degree. C. for two hours, then filtered and
stored at -10.degree. C.
[0348] b. Monoazo adduct
[0349] To a 1000 ml flask, fitted with a mechanical stirrer, are
added 40 g of sodium hydroxide dissolved in 200 ml of methanol and
32.4 g of 2-.alpha.-cumyl-4-tert-octylphenol in 50 ml of xylene.
The solution is cooled to 5.degree. C. and the diazo solution of
4-amino-nitro-benzotrifl- uoride prepared in part a. is added at 0
to 5.degree. C. over a two-hour period. Then 100 ml of xylene are
added and the organic layer is washed with water, aqueous
hydrochloride acid, water, aqueous sodium bicarbonate solution and
finally water. The solvent is removed under reduced pressure and
the residue is purified by chromatography (silica gel,
heptane:ethyl acetate 95:5) to yield 42.1 g of the adduct product
as a dark red paste.
[0350] c. Reduction of the monoazo adduct
[0351] A 1000 ml flask is charged with 20 g of sodium hydroxide, 40
ml of water, 42.1 g of the monoazo adduct prepared in part b. and
400 ml of ethanol. The mixture is warmed to 80.degree. C. and 27 g
of formamidine sulfinic acid is added in portions with stirring.
After 1.5 hours, the solution is cooled to room temperature and 100
ml of water are added. The pH is adjusted to pH 7 with concentrated
hydrochloric acid. The ethanol is removed under vacuum and the
water layer is extracted with methylene chloride. The solvent is
then evaporated in vacuo and the residue is purified by
chromatography (silica gel, heptane:tolunen 9:1) and crystallized
from ethanol. The title compound is obtained in a yield of 5.6 g as
a pale yellow solid melting at 119-121.degree. C.
EXAMPLE 2
5-Fluoro-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benzotriazole
[0352] The title compound is prepared according to the general
procedure of Example 1 using 31.2 g of 4-fluoro-2-nitroaniline. In
part c of the procedure, an additional 9 g of formamidine sulfinic
acid is required to complete the reduction. Purification of the
crude product on silica gel (heptane:toluene, 1:1) yields 4.5 g of
the title compound as a off-white solid. Further purification by
recrystallization from acetonitrile:toluene provides 1.1 g of the
title compound melting at 93-96.degree. C.
EXAMPLE 3
5-Chloro-2-(2-hydroxy-3-(.alpha.-cumyl-5-tert-octylphenyl)-2H-benzotriazol-
e
[0353] The general procedure of Example 1 parts a and b is followed
to prepare the monoazo intermediate of making the title compound
from 339.3 g of 4-chloro-2-nitro-aniline. The crude product is
purified by recrystallization from methanol to yield 70.9 g of deep
red monoazo adduct.
Reduction of the Monoazo Adduct
[0354] A mixture of 11.8 g of sodium hydroxide and 138 g of
2-butanol is heated to 95.degree. C. A solution of 60.1 g of the
above monoazo adduct and 1.3 g of 2,3-dichloro-1,4-naphtho-quinone
in 90 g of 2-butanol is added over a 90 minute period with
stirring. The reaction mixture is heated to remove the 2-butanone
byproduct with additional 2-butanol added to replace the
distillate. The reaction mixture is cooled to 85.degree. C., washed
with 2.5 N sulfuric acid and brine and then concentrated. The
residue is recrystallized from methanol:xylene to yield 45.6 g of
the title compound as a light yellow solid melting at
104-105.degree. C.
EXAMPLE 4
5-Phenylthio-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benzotria-
zole
[0355] To a stirred mixture of 75 g of
5-chloro-2-(2-hydroxy-3-(.alpha.-cu-
myl-5-tert-octyl-phenyl)-2H-benzotriazole and 105 g of
N-methylpyrrolidone heated at 90.degree. C. is added first 44.3 g
of 45% aqueous potassium hydroxide solution over a 15-minute period
then 20.4 g of thiophenol over another 15 minutes. The reaction
mixture is then heated at 170-175.degree. C. for four hours with
water being removed by distillation. After cooling to 100.degree.
C., xylene and water are added and the resultant mixture is made
acidic with 15% aqueous hydrogen chloride solution. The organic
layer is separated and washed with water and then concentrated. The
crude product residue is recrystallized from methanol to yield 82 g
of the tide compound as a pale yellow solid melting at
124-125.degree. C.
EXAMPLE 5
5-Benzenesulfonyl-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benz-
otriazole
[0356] A 1000 mL flask is charged with 75.2 g of
5-phenylthio-2-(2-hydroxy-
-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benzotriazole, prepared in
Example 4, 102 g of xylene, 0.9 g of sodium tungstate dihydrate and
18.4 g of formic acid. The mixture is heated to 50.degree. C. To
this stirred mixture is slowly added 36.3 g of 50% hydrogen
peroxide so that the temperature does not exceed 85.degree. C.
Additional xylene and water are then added. The organic layer is
separated, washed with aqueous sodium sulfite, then twice with
water and concentrated. The crude product residue is recrystallized
from methanol to yield 75.2 g of the title compound as a light
yellow solid melting at 170-171.degree. C.
EXAMPLE 6
5-Nonylthio-2-(2-hydroxy-3-(.alpha.-cumyl-5-tert-octylphenyl)-2H-benzotria-
zole
[0357] Using the procedure of Example 4 with 30 g of
5-chloro-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benzotriazol-
e and 17.6 g of nonyl mercaptan, the title compound is
prepared.
EXAMPLE 7
5-Nonylsulfonyl-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benzot-
riazole
[0358] 5-Nonylthio-2-(2-hydroxy-3-.alpha.-cumyl-5
-tert-octylphenyl)-2H-be- nzotriazole, prepared in Example 6, is
oxidized to the sulfone without purification of the thio
intermediate using 8.7 g of formic acid, 0.7 g of sodium tungstate
dihydrate and 17.6 g of 50% hydrogen peroxide to yield the title
compound as a yellow resin exhibiting a molecular ion of m/e
631.
EXAMPLE 8
5-Chloro-2-(2-hydroxy-3-phenyl-5-tert-octylphenyl)-2H-benzotriazole
[0359] The general procedure of Example 1 parts a and b are used to
prepare the monoazo intermediate for the title compound from
4-chloro-2-nitroaniline and 2-phenyl-4-tert-octylphenol. The crude
product is purified by recystallization from methanol to yield a
deep red monoazo adduct.
[0360] The title compound is prepared according to the reduction
procedure of Example 3 from 65 g of the monoazo adduct prepared
above, 19.9 g of sodium hydroxide and 2.4 g of
2,3-dichloro-1,4-naphthoquinone. The crude product is purified by
chromatography on silica gel (hexane:ethyl acetate, 5:1) yielding a
fraction which is predominantly the title compound exhibiting a
molecular ion of m/e 433.
EXAMPLE 9
5-Phenylthio-2-(2-hydroxy-3-phenyl-5-tert-octylphenyl)-2H-benzotriazole
[0361] The title compound is prepared according to the procedure of
Example 4 from 20 g of the compound of Example 8, 20.4 g of 45%
aqueous potassium hydroxide, 10.3 g of thiophenol and 100 g of
N-methylpyrrolidone. The title compound is an oil purified by
chromatography on silica gel using toluene as eluent.
EXAMPLE 10
5-Benzenesulfonyl-2-(2-hydroxy-3-phenyl-5-tert-octylphenyl)-2H-benzotriazo-
le
[0362] The title compound is prepared according to the procedure of
Example 5 from 20 g of the thio compound of Example 9, 6.4 g of
formic acid, 15.0 g of 50% hydrogen peroxide and 0.6 g of sodium
tungstate dihydrate. Recrystallization of 2.5 g of crude material
from xylene/methanol yields 2.0 g of the purified title compound as
a light yellow powder melting at 204-206.degree. C.
EXAMPLE 11
Mixture of
5-Chloro-2-(2-hydroxy-3,5-dialkylphenyl)-2H-benzotriazole (alkyl
being independently C.sub.4, C.sub.8, C.sub.12 and C.sub.16)
[0363] A mixture of 65.4 g of
5-chloro-2-(2-hydroxy-3,5-dialkylphenyl)-2H-- benzo-triazole, 45 mL
of dodecene and 13 mL of methane sulfonic acid is heated to
170.degree. C. under nitrogen. An additional 135 mL of dodecene is
added over a 4.5 hour period. The reaction mixture is allowed to
cool to 100.degree. C. and then quenched with 400 g of crushed ice
and extracted thrice with ethyl acetate. The organic layers are
combined, washed with water, aqueous sodium bicarbonate, water
again and brine, dried over anhydrous magnesium sulfate and finally
concentrated. The polymeric residue is removed by bulb to bulb
distillation under vacuum at 0.2 mm and up to 210.degree. C.
Unreacted starting material is then removed by distillation (at
0.01 mm, 160.degree. C.) to give 45 g of the title mixture as a
yellow oil.
EXAMPLE 12
Mixture of
5-Phenylthio-2-(2-hydroxy-3,5-dialkylphenyl)-2H-benzotriazole
(alkyl being independently C.sub.4, C.sub.8, C.sub.12 and
C.sub.16)
[0364] The title mixture is prepared according to the procedure of
Example 4 using 40 g the mixture of Example 11, 11.2 g of potassium
hydroxide and 12.3 mL of thiophenol.
EXAMPLE 13
Mixture of
5-Benzenesulfonyl-2-(2-hydroxy-3,5-dialkylphenyl)-2H-benzotriaz-
ole (alkyl being independently C.sub.4, C.sub.8, C.sub.12 and
C.sub.16)
[0365] A mixture of the crude product of Example 12, 350 mL of
isopropanol, 14.7 mL of formic acid and 1.8 mL of concentrated
sulfuric acid are heated to reflux and 30 mL of 50% hydrogen
peroxide is added dropwise over a two-hour period. After an
additional three hours at reflux, the reaction mixture is cooled
and 10% aqueous sodium sulfite and aqueous sodium bicarbonate are
added. The isopropanol is evaporated and the residue is extracted
with methylene chloride. The organic layer is washed with water and
then dried over anhydrous magnesium sulfate. The solution is
concentrated to leave 45 g of crude product as a viscous prange
oil. Some 30 g of this crude product is purified by chromatography
on silica gel (heptane:ethyl acetate, 4:1) to yield 28.9 g of the
title mixture as a yellow oil.
EXAMPLE 14
5-Diphenylphosphinyl-2-(2-hydroxy-3,5-tert-butylphenyl)-2H-benzotriazole
[0366] To a flame-dried 500 mL three-necked round-bottomed flask
equipped with a condenser, magnetic stirrer and thermometer are
charged 100 mL of dimethyl sulfoxide, 7.41 g (0.066 mol) of
potassium tert-butoxide and 11.17 g (0.060 mol) of
diphenyl-phosphine via a syringe. A slurry of 10.56 g (0.030 mol)
of 5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H--
benzotriazole in 50 mL of dimethyl sulfoxide is added all at once
to the red mixture. The resultant brown solution is stirred at
135.degree. C. for 3.5 hours and then cooled to room temperature.
The mixture is quenched with a portion of saturated ammonium
chloride solution and ethyl acetate is then added. The organic
layer is separated and washed thrice with water, once with brine
and then dried over anhydrous magnesium sulfate. To the solution is
added 50% hydrogen peroxide resulting in an exotherm. The mixture
is allowed to sit for 30 minutes, then washed once with 10% sodium
metabisulfite solution thrice with saturated sodium bicarbonate
solution once with brine and finally dried over anhydrous magnesium
sulfate. The mixture is filtered with a plug of silica gel and the
solvent is removed under reduced pressure to yield 8.0 g of a crude
yellow solid. The crude product is treated with medium pressure
chromatography using heptane:ethyl acetate, 1:1 to afford 4.2 g
(27% yield) of the title compound as a yellow solid melting at
98-100.degree. C.
EXAMPLE 15
5-Diphenylphosphinyl-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-b-
enzotriazole
[0367] Following the procedure of Example 14, the title compound is
prepared when
5-chloro-2-(2-hydroxy-3-(.alpha.-cumyl-5-tert-octylphenyl)--
2H-benzotriazole is used as the starting benzotriazole
intermediate.
EXAMPLES 16-26
[0368] Following the general procedure of Example 1, the following
additional 2H-benzotriazoles of formula I' are prepared.
3 Example G.sub.2 E.sub.1 E.sub.2 16 CF.sub.3 phenyl tert-octyl 17
CF.sub.3 .alpha.-cumyl tert-butyl 18 CN .alpha.-cumyl tert-octyl 19
CN .alpha.-cumyl nonyl 20 CN .alpha.-cumyl tert-butyl 21
COOCH.sub.3 .alpha.-cumyl dodecyl 22 F phenyl tert-octyl 23
CF.sub.3 .alpha.-cumyl nonyl 24 CF.sub.3 .alpha.-cumyl dodecyl 25
CON(Bu).sub.2 .alpha.-cumyl tert-octyl 26 COOCH.sub.3 phenyl
tert-octyl
EXAMPLE 27
5-Octylthio-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benzotriaz-
ole
[0369] Using the procedure of Example 6 with
5-chloro-2-(2-hydroxy-3-.alph-
a.-cumyl-5-tert-octylphenyl)-2H-benzotriazole and octyl mercaptan,
the title compound is prepared.
EXAMPLE 28
5-Octylsulfonyl-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benzot-
riazole
[0370]
5-Octylthio-2-(2-hydroxy-3-(.alpha.-cumyl-5-tert-octylphenyl)-2H-be-
nzotriazole, prepared in Example 27, is oxidized to the sulfone
without purification of the thio intermediate using the general
method of Example 7.
EXAMPLE 29
5-Chloro-2-(2,4-dihydroxyphenyl)-2H-benzotriazole
[0371] Following the general procedure of Example 1, parts a &
b, the monoazo intermediate of the title compound is prepared from
17.3 g of 4-chloro-2-nitroaniline to yield 34.7 g of a deep red
monoazo adduct wetcake.
Reduction of the Monoazo Adduct
[0372] A mixture of 20 g of sodium hydroxide, 500 mL of water and
26.3 of the monoazo adduct wetcake prepared above is heated to
30.degree. C. Zinc powder (33.0 g) is added incrementally over two
hours. At the end of this addition, 180 g of 40% aqueous sodium
hydroxide solution is added dropwise over one hour. The mixture is
stirred at ambient temperature for 96 hours. The zinc residue is
removed by filtration. The aqueous solution is neutralized to pH
5-6 and the resulting slurry is filtered. The resulting filter case
is washed well with water and dried to yield 22.5 g of crude
product. The crude product is purified by Soxhlet extraction with
acetone to give 9.6 g of the title compound.
EXAMPLE 30
5-Chloro-2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole
[0373] A mixture of 6.5 g of
5-chloro-2-(2,4-dihydroxyphenyl)-2H-benzotria- zole, 7.1 g of
1-bromooctane, 5.2 g of anhydrous potassium carbonate and 100 mL of
acetone is refluxed for 24 hours. To the resulting mixture, about
100 mL of water and ethyl acetate are added, and 10.6 g of crude
product is isolated. Column chromatography using petroleum ether
yields 0.9 g of the title compound whose structure is confirmed by
Hnmr and mass spectrometry.
EXAMPLE 31
5-Trifluoromethyl-2-(2,4-dihydroxyphenyl)-2H-benzotriazole
[0374] Following the general procedure of Example 29, the title
compound is prepared from 10.3 g of 4-amino-3-nitrobenzotrifluoride
to give 6.4 g of the title compound whose structure is confirmed by
Hnmr.
EXAMPLE 32
5-Trifluoromethyl-2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole
[0375] The title compound is prepared following the general
procedure of Example 30 from 5.6 g of
5-trifluoromethyl-2-(2,4-dihydroxyphenyl)-2H-ben- zotriazole. The
crude product is purified by column chromatography to yield 1.1 g
of the title compound as a white solid melting at 79-81.degree. C.
The structure is confirmed by Hnmr and mass spectrometry.
EXAMPLE 33
5-Trifluoromethyl-2-[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-2H-ben-
zotriazole
[0376] A mixture of 2.3 g of
5-trifluoromethyl-2-(2,4-dihydroxyphenyl)-2H-- benzotriazole
prepared in Example 31, 1.3 mL of butyl glycidyl ether and 100 mg
of ethyl triphenyl-phosphonium bromide in 50 mL of xylene is heated
to reflux under nitrogen for 14 hours. Water (25 mL) and 25 mL of
ethyl acetate are added and 3 g of the crude product is isolated.
Recrystallization from heptane give 2.1 g of the title compound
whose structure is confirmed by nmr.
EXAMPLE 34
5-Trifluoromethyl-2-(2-hydroxy-4-aminophenyl)-2H-benzotriazole
[0377] The title compound is prepared following the general
procedures of Example 1 and Example 29 starting with
4-amino-3-nitrobenzotrifluoride and 3-aminophenol. The structure of
the product is confirmed by nmr.
EXAMPLE 35
5-Trifluoromethyl-2-[2-hydroxy-4-(2-ethylhexanoylamino)phenyl]-2H-benzotri-
azole
[0378] To a mixture of 4 g of
5-trifluoromethyl-2-(2-hydroxy-4-aminophenyl- )-2H-benzotriazole
and 1.4 g of triethylamine in 75 mL of toluene is added dropwise a
mixture of 2-ethylhexanoyl chloride in 125 mL of toluene. The
resulting mixture is treated with 100 mL of water and the crude
product formed is purified by column chromatography to give 1.9 g
of the title compound melting at 179-181.degree. C. The structure
is confirmed by nmr.
EXAMPLE 36
5-Carbomethoxy-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benzotr-
iazole
a. Esterification of 4-amino-3-nitrobenzoic Acid
[0379] To a 2 L 3-necked flask fitted with a mechanical stirrer are
added 700 mL of methanol, 20 g of xylene, 14 g concentrated
sulfuric acid and 100 g of 4-amino-3-nitrobenzoic acid. The
solution is heated to reflux for 33 hours. The mixture is cooled to
35.degree. C. and neutralized to pH 7.8. Water (1 L) is added, the
solid collected and washed with 500 ml to give after drying
overnight 100.9 g of methyl 4-amino-3-nitrobenzoate.
b. Diazotization of methyl 4-amino-3-nitrobenzoate
[0380] To a 1 L 3-necked flask fitted with a mechanical stirrer is
added 177 g of 96% sulfuric acid and then slowly over 90 minutes 11
g of sodium nitrite. The mixture is warmed to 30.degree. C. to
initiate the reaction. The temperature is kept below 70.degree. C.
The mixture is then cooled to 15.degree. C. and 30 g of methyl
4-amino-3-nitrobenzoate is added over two hours keeping the
temperature between 15-20.degree. C. The mixture is cooled to
0.degree. C. and 200 g of ice is added to make the solution
suitable for the coupling reaction to form a monoazo compound.
c. Monoazo Adduct
[0381] To a 2 L 3-necked flask fitted with a mechanical stirrer and
addition funnel are added 52 g of
2-(.alpha.-cumyl-4-tert-octylphenol, 20 g of water, 315 g of
methanol, 7 g of xylene and 150 g of sodium hydroxide. The mixture
is cooled to -5.degree. C. and the diazonium salt solution prepared
is step b. is added over a two hour period with cooling to keep the
temperature below 3.degree. C. After the diazonium salt solution is
added, the pH is adjusted to 6.5-7.0. The mixture is poured into
500 mL of xylene and washed thrice with 500 mL of water at
60.degree. C. The xylene is removed by distillation to give 186 g
of the monoazo adduct containing residual xylene.
d. Reduction of the Monoazo Adduct
[0382] To a 500 mL flask fitted with a mechanical stirrer is added
the 186 g of monoadduct prepared in step c., 125 g of 2-butanol and
1.7 g of 2,3-dichloro-1,4-naphthoquinone. The mixture is heated to
90.degree. C. and the resulting solution is then charged to the
addition funnel on a separate flask. In said second flask are added
175 g of 2-butanol and 18.6 g of sodium hydroxide, The flask is
heated to 95.degree. C. and the monoazo solution is added over two
hours while distilling off methyl ethyl ketone and 2-butanol.
2-Butanol (100 g) is added and an azeotrope is distilled off. The
mixture is then cooled and 300 g of xylene and 200 mL of water are
added. The pH is adjusted to 7-7.5 with 20% sulfuric acid. At
60.degree. C., the aqueous phase is separated and the organic phase
washed twice with 200 mL of water. The xylene is removed by
distillation and the residue formed is crystallized from methanol
to give 8.8 g of the title compound melting at 141-143.degree.
C.
EXAMPLE 37
5-[N,N-Di-n-butylcarbamoyl-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octyl)pheny-
l]-2H-benzotriazole
a. Saponification of
5-Carbomethoxy-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-oc-
tylphenyl)-2H-benzotriazole
[0383] To a 250 mL 3-necked flask equipped with a mechanical
stirrer, thermometer, condenser and nitrogen inlet is added 1.8 g
of potassium hydroxide and 40 mL of methanol. The mixture is warmed
to 40.degree. C. to dissolve the potassium hydroxide. To this
solution is added 2.7 g of
5-carbomethoxy-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-benzot-
riazole, prepared in Example 36, in 40 mL of methanol. The reaction
mixture is refluxed for six hours. The mixture is then cooled and
acidified with hydrochloric acid. Ether and ethyl acetate are
added, and the organic layer is separated and dried over anhydrous
sodium sulfate. After vacuum stripping of the solvent, 2.5 g of
5-carboxy-2-(2-hydroxy-3--
.alpha.-cumyl-5-tert-octylphenyl)-2H-benzotriazole is isolated.
b.
5-Chlorocarbonyl-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphenyl)-2H-be-
nzotriazole
[0384] The 2.5 g of
5-carboxy-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octylphe-
nyl)-2H-benzo-triazole, prepared in step a., are placed in a 250 mL
flask equipped with a stirrer, thermometer, reflux condenser,
Dean-Stark trap and nitrogen inlet. Toluene (100 mL) is added and
the mixture is reflux to remove any traces of water. The mixture is
then cooled and 0.76 g of oxalyl chloride in 15 mL of toluene is
added. The reaction mixture is heated slowly to 60.degree. C. and
held at 60-65.degree. C. for eight hours till all the hydrogen
chloride is expelled to give the acid chloride title compound.
c.
5-[N,N-Di-n-butylcarbamoyl-2-(2-hydroxy-3-.alpha.-cumyl-5-tert-octyl)ph-
enyl]-2H-benzotriazole
[0385] To a 500 mL flask equipped with a mechanical stirrer, drying
tube, thermometer and dropping funnel are added 0.8 g of
di-n-butylamine, 6 mL of pyridine and 25 mL of toluene, The mixture
is cooled to 0.degree. C. and the acid chloride solution prepared
in step b. is placed in the dropping funnel and added to the
reaction mixture over a 30-minute period at -5.degree. C. to
-10.degree. C. The reaction mixture is stirred at that temperature
for 1.5 hours and then held at ambient temperature overnight. The
mixture was filtered and then vacuum stripped to give 3.0 g of
crude solids. The solid product is chromatographed to provide 1.2 g
of the title compound as a tan solid melting at 131-133.degree. C.
The structure is confirmed by nmr and mass spectrometry m/z
596.
EXAMPLE 38
5-Trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole
[0386] The title compound is prepared according to general
procedure of Example 1 the diazo compound of
4-amino-3-nitrobenzotrifluoride and 4-tert-octylphenol, and which
is purified by chromatography on silica gel. Recrystallization of
the product from either heptane or methanol yields the title
compound as a near white solid melting at 80-81.degree. C.
EXAMPLE 39
[0387] To ascertain the effect on thermal durability and loss rate
from a high solids thermoset acrylic coating of various
2H-benzotriazole UV absorbers substituted by a variety of electron
withdrawing and electron donating groups, the following tests are
carried out.
[0388] A high solids thermoset acrylic clear coat is prepared by
mixing an experimental acrylic polyol resin and
hexamethoxymethylmelamine (Resimene.RTM. 747, Monsanto) at a solids
ratio of 60/40. The dodecylbenzene sulfonic acid catalyst
(Nacure.RTM. 5225; King Industries) is added at 0.70% by weight. A
flow aid Modaflow.RTM. (Monsanto) is added at 0.25% by weight to
form a model acrylic melamine resin system.
[0389] The model clear coat is reduced with xylene to a viscosity
of 26-27 second using a Zahn #2 cup and applied via a conventional
air spray at 50 psi (3.5 Kg/cm.sup.2) over a 1"33 3" (2.54
cm.times.7.62 cm) quartz slide. Cure is achieved by baking the
slide for 30 minutes at 260.degree. F. (127.degree. C.). The clear
coat is stabilized with 1% by weight of a hindered amine light
stabilizer, bis-(1-octyloxy-2,2,6,6-tetramethylpiper- idin-4-yl)
sebacate, (TINUVIN.RTM. 123, Ciba-Geigy). The various test
benzotriazole UV absorbers are incorporated at the 5 mmol % by
weight in the clear coat. The film thickness on the quartz slides
range from 1.15 to 1.41 mils (0.029 to 0.036 mm).
[0390] The films on the quartz slides are weathered according to
the following conditions in Xenon Arc Weather-Ometer with a
controlled irradiance at 6500 W, using inner quartz and outer
borosilicate S-type filter. The irradiation cycle is as follows: 40
minutes of straight irradiation with no water spray, followed by 20
minutes of light plus front spray, followed by 60 minutes of light
irradiation and finally by 60 minutes dart plus rear spray
(condensation). The setting is at 0.55 W/M.sup.2 at 340 nm, 1.98
kJ/hour. In the light cycle the black panel temperature is
controlled at 70.+-.2.degree. C. The relative humidity in the light
cycle is in the range of 50-55% and in the dark cycle 100%. The
absorbance of the long wavelength UV band as a function of Xenon
arc weathering hours are recorded in the table below.
[0391] To follow the loss of UV absorbers from the clear coats, UV
spectra are measured initially and after weathering at regular time
intervals. The UV spectrophotometer measures absorbance linearly up
to 5.5 absorbance units using a reference beam attenuation
technique.
[0392] It is assumed that the degradation products from the UV
absorber do not contribute to the UV spectrum. This is tested by
following the ratio of absorbance of the band at about 300 nm and
the band at about 340 nm. The ratio does not change upon weathering
the sample, This suggests that the UV spectrum of the weathered
films correspond to the amount of UV absorber remaining in the film
with very little if any contribution to the spectrum by photo
degradants.
[0393] The data in the table below are based on formula A after
1211 hours of exposure of the clear coats containing the test
benzotriazole UV absorbers.
4 Units Absorbance Compound Loss G.sub.2 R.sub.1 R.sub.2* A 1.7982
hydrogen --PO(OEt).sub.2 tert-octyl B 1.6300 hydrogen nitro
tert-octyl C 1.4863 phenyl-S-- tert-butyl group I D 1.4002 hydrogen
hydrogen group II E 1.1872 methoxy tert-butyl methyl F 0.5259
hydrogen tert-butyl group II G 0.4527 hydrogen hydrogen
.alpha.-cumyl H 0.4420 hydrogen tert-butyl group I I 0.4299
hydrogen tert-octyl .alpha.-cumyl J 0.4134 hydrogen hydrogen
tert-octyl K 0.3777 hydrogen tert-octyl tert-octyl L 0.3712
hydrogen tert-butyl CH.sub.2CH.sub.2CH.sub.2OH M 0.3433 hydrogen
.alpha.-cumyl group II N 0.3098 cyano tert-butyl tert-butyl O
0.2689 phenyl-SO.sub.2-- tert-butyl group I P 0.2576 hydrogen
.alpha.-cumyl .alpha.-cumyl Q 0.2492 hydrogen .alpha.-cumyl
tert-octyl *Group I is --CH.sub.2CH.sub.2COOC.sub.8H.sub.1- 7 Group
II is --CH.sub.2CH.sub.2COOCH.sub.3
[0394] Inspection of these data leads to some clear conclusions
about the photostability of 2H-benzotriazole UV absorbers and about
the nature of the substitution which will affect that
photostability.
[0395] Increased photostability occurs when R.sub.1 is
.alpha.-cumyl or phenyl and when G.sub.2 is an electron withdrawing
group such as phenyl-sulfonyl or cyano.
[0396] The nature of the R.sub.2 group has less influence on the
photostability of the benzotriazole UV absorbers.
[0397] From these observations, then an idealized benzotriazole UV
absorber might theoretically be designed where G.sub.2 is an
electron withdrawing group, R.sub.1 is an effective bulky group,
and R.sub.2 is a thermally stable moiety. One such idealized
compound might be a benzotriazole where G.sub.2 is phenylsulfonyl,
R.sub.1 is .alpha.-cumyl and R.sub.2 is tert-octyl. This
benzotriazole is generically claimed in U.S. Pat. No. 5,280,124.
The data given in Example 30 below confirms this prediction and
this "idealized" compound does indeed exhibit a very low loss rate
well below the present state of the art.
EXAMPLE 40
[0398] Following the general procedure of Example 39, a number of
additional benzotriazole test compounds are incorporated into a
high solids thermoset acrylic melamine resin at such concentrations
between 1.93 and 3% by weight to give equal molar concentrations of
test benzotriazole in equal film thickness, and sufficient to give
a starting absorbance of approximately 2.0 absorbance units.
[0399] The test discs are exposed in a Xenon-Arc Weather-Ometer at
X180 cycle (0.45 Watts/M.sup.2). The initial UV absorbance is
measured followed by measurements at roughly 250 hour intervals for
the first 2000 hours and every 500 hours thereafter. Each clear
coat also contains 1% by weight of a hindered amine light
stabilizer, bis-(1-octyloxy-2,2,6,6-tetr- amethylpiperidin-4-yl)
sebacate, as well.
[0400] The data in the table below are based on compounds of
formula A after 1253 hours of exposure of the clear coats
containing the test benzotriazole UV absorbers.
5 Units Absorbance Compound Loss G.sub.2 R.sub.1 R.sub.2 R 0.2424
hydrogen phenyl .alpha.-cumyl Q 0.2351 hydrogen .alpha.-cumyl
tert-octyl S 0.1271 CF.sub.3 .alpha.-cumyl tert-octyl T 0.1827
phenyl-SO.sub.2 tert-butyl tert-butyl
[0401] The data in the table below are based on compounds of
formula A after 1489 hours of exposure of the clear coats
containing the test benzotriazole UV absorbers.
6 Units Absorbance Compound Loss G.sub.2 R.sub.1 R.sub.2 R 0.3724
hydrogen phenyl .alpha.-cumyl Q 0.287 hydrogen .alpha.-cumyl
tert-octyl S 0.1547 CF.sub.3 .alpha.-cumyl tert-octyl T 0.2654
phenyl-SO.sub.2 tert-butyl tert-butyl
[0402] The data in the table below are based on compounds of
formula A after 2521 hours of exposure of the clear coats
containing the test benzotriazole UV absorbers.
7 Units Absorbance Compound Loss G.sub.2 R.sub.1 R.sub.2 R 0.4824
hydrogen phenyl .alpha.-cumyl Q 0.4054 hydrogen .alpha.-cumyl
tert-octyl S 0.2192 CF.sub.3 .alpha.-cumyl tert-octyl T 0.3570
phenyl-SO.sub.2 tert-butyl tert-butyl
[0403] It is clear from the three tables above that Compounds S and
especially T which have an electron withdrawing group at the
5-position of the benzo ring are significantly more durable than
benzotriazoles which do not have such a group on the benzo
ring.
[0404] The data in the table below are based on compounds of
formula A after 1264 hours of exposure of the clear coats
containing the test benzotriazole UV absorbers.
8 Units Absorbance Compound Loss G.sub.2 R.sub.1 R.sub.2 Q 0.4054
hydrogen .alpha.-cumyl tert-octyl S 0.2192 CF.sub.3 .alpha.-cumyl
tert-octyl T 0.3570 phenyl-SO.sub.2 tert-butyl tert-butyl U 0.0944
phenyl-SO.sub.2 .alpha.-cumyl tert-octyl V 0.1719 chloro
.alpha.-cumyl tert-octyl W 0.1655 fluoro .alpha.-cumyl tert-octyl X
0.1796 hydrogen phenyl tert-octyl
[0405] The data in the table below are based on compounds of
formula A after 1518 hours of exposure of the clear coats
containing the test benzotriazole UV absorbers.
9 Units Absorbance Compound Loss G.sub.2 R.sub.1 R.sub.2 Q 0.2662
hydrogen .alpha.-cumyl tert-octyl S 0.1116 CF.sub.3 .alpha.-cumyl
tert-octyl T 0.2423 phenyl-SO.sub.2 tert-butyl tert-butyl U 0.1114
phenyl-SO.sub.2 .alpha.-cumyl tert-octyl V 0.1955 chloro
.alpha.-cumyl tert-octyl W 0.1668 fluoro .alpha.-cumyl tert-octyl X
0.2220 hydrogen phenyl tert-octyl
[0406] The data in these tables clearly show that benzotriazoles
substituted by an electron withdrawing group on the benzo ring,
particularly a group such as trifluoromethyl or phenyl-sulfonyl,
are especially durable as measured by low loss rate absorbance
values after exposure to actinic radiation. Compounds S, U, V and W
are especially durable and fit the profile proposed above. Indeed,
the prediction that Compound U would be particularly durable is
borne out by the data above. Inspection of the data for compounds T
and U shows the added beneficial effect of having an effective
bulky group such as .alpha.-cumyl at the R.sub.1 position compared
to a mere alkyl moiety such as tert-butyl at that position.
* * * * *