U.S. patent application number 09/928098 was filed with the patent office on 2002-03-07 for benzocycle-substituted triazine and pyrimidine ultraviolet light absorbers.
This patent application is currently assigned to CYTEC TECHNOLOGY CORP.. Invention is credited to Fischer, Robert G., Gupta, Ram B., Jakiela, Dennis J..
Application Number | 20020028937 09/928098 |
Document ID | / |
Family ID | 27376527 |
Filed Date | 2002-03-07 |
United States Patent
Application |
20020028937 |
Kind Code |
A1 |
Gupta, Ram B. ; et
al. |
March 7, 2002 |
Benzocycle-substituted triazine and pyrimidine ultraviolet light
absorbers
Abstract
This invention relates generally to benzocycle-substituted
pyrimidines and triazines and the use thereof to protect against
degradation by environmental forces, inclusive of ultraviolet
light, actinic radiation, oxidation, moisture, atmospheric
pollutants and combinations thereof. The new class of
benzocycle-substituted pyrimidines and triazines comprises a
benzocycle attached to the triazine or pyrimidine ring, and
preferably an additional aryl ring containing a hydroxyl group,
either free or blocked to form a latent stabilizer, ortho- to the
point of attachment to the triazine or pyrimidine ring. These
materials may, under the appropriate circumstances, be bonded to
formulations comprising coatings, polymers, resins, organic
compounds and the like via reaction of the bondable functionality
with the materials of the formulation. A method for stabilizing a
material by incorporating such benzocycle-substituted pyrimidines
and triazines is also disclosed.
Inventors: |
Gupta, Ram B.; (Stamford,
CT) ; Jakiela, Dennis J.; (Orange, CT) ;
Fischer, Robert G.; (Fairfield, CT) |
Correspondence
Address: |
CYTEC TECHNOLOGY Corp.
300 Delaware Avenue
Wilmington
DE
19801
US
|
Assignee: |
CYTEC TECHNOLOGY CORP.
|
Family ID: |
27376527 |
Appl. No.: |
09/928098 |
Filed: |
August 10, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09928098 |
Aug 10, 2001 |
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09335790 |
Jun 18, 1999 |
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6297377 |
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60090260 |
Jun 22, 1998 |
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60108895 |
Nov 17, 1998 |
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Current U.S.
Class: |
544/215 ;
524/100 |
Current CPC
Class: |
C07D 251/24 20130101;
C08K 5/3492 20130101 |
Class at
Publication: |
544/215 ;
524/100 |
International
Class: |
C08K 005/3492; C07D
251/00 |
Claims
What is claimed is:
1. A composition comprising (a) a compound of Formula I 49wherein T
is a direct bond, carbon, oxygen, nitrogen, sulfur or a functional
group containing these elements; T' is oxygen, nitrogen, sulfur or
carbon; X is independently selected from hydrogen and a blocking
group; each of R.sup.1 and R.sup.2 is independently a hydrocarbyl
group, a functional hydrocarbyl group, hydroxy, alkoxy, hydrogen,
halogen, cyano, or isocyano, wherein the hydrocarbyl has 1 to 24
carbon atoms; each of Y, R.sup.3 and R.sup.4 are independently a
hydrogen, hydrocarbyl group, a functional hydrocarbyl group,
halogen, hydroxyl, cyano, --O(hydrocarbyl), --O(functional
hydrocarbyl), --N(hydrocarbyl).sub.2, --N(functional
hydrocarbyl).sub.2, --N(hydrocarbyl)(functional hydrocarbyl),
--S(hydrocarbyl), --S(functional hydrocarbyl),
--SO.sub.2(hydrocarbyl), --SO.sub.2(functional hydrocarbyl),
--SO.sub.3(hydrocarbyl), --SO.sub.3(functional hydrocarbyl),
--CO.sub.2(hydrocarbyl), --CO.sub.2(functional hydrocarbyl),
--CO(hydrocarbyl), --CO(functional hydrocarbyl),
--OCO(hydrocarbyl), --OCO(functional hydrocarbyl), --CONH.sub.2,
--CON H(hyrdocarbyl), --CON H(functional hyrdocarbyl),
--CON(hydrocarbyl).sub.2, --CON(hydrocarbyl)(functional
hyrdocarbyl), --CON(functional hydrocarbyl).sub.2, wherein the
hydrocarbyl or functional hydrocarbyl may be the same or different
and has 1 to 24 carbon atoms; Z is Y, 50wherein L is hydrogen, a
hydrocarbyl group of 1 to 24 carbon atoms, or a functional
hydrocarbyl group of 1 to 24 carbon atoms; X is independently
selected from hydrogen and a blocking group; and R.sup.3 and
R.sup.4 are independently hydrogen, hydrocarbyl, functional
hydrocarbyl, halogen, hydroxyl, --O(hydrocarbyl), --O(functional
hydrocarbyl), --S(hydrocarbyl), --SO.sub.2(hydrocarbyl),
--SO.sub.3(hydrocarbyl), --CO.sub.2(hydrocarbyl),
--CO(hydrocarbyl), --OCO(hydrocarbyl), --N(hydrocarbyl).sub.2,
--S(functional hydrocarbyl), --SO.sub.2(functional hydrocarbyl),
--SO.sub.3(functional hydrocarbyl), --CO.sub.2(functional
hydrocarbyl), --CO(functional hydrocarbyl), --OCO(functional
hydrocarbyl), --N(functional hydrocarbyl).sub.2 or cyano wherein
the hydrocarbyl or functional hydrocarbyl may be the same or
different and has 1 to 24 carbon atoms; each G is independently a
direct bond, nitrogen, sulfur, oxygen, or functional groups
containing these elements; each of m, n, and o is independently an
integer between 0 and 4, provided that when both G are direct
bonds, the sum of m, n and o is between 2 and 10, and that when one
G is a direct bond, the sum of m, n and o is between 1 and 9, and
when neither G is a direct bond, the sum of m, n and o is between 0
and 8; and (b) at least one other additive selected from the group
consisting of: UV-absorbers and light stabilizers, and
antioxidants.
2. The composition of claim 1 wherein said at least one other
additive is selected from the group consisting of
2-(2'-hydroxyphenyl)benzotriazoles, oxamides,
2-(2-hydroxphenyl)-1,3,5-triazines, 2-hydroxybenzophenones,
sterically hindered amines and hindered phenol antioxidants.
3. The composition of claim 1 wherein said at least one additive is
selected from the group consisting of:
2-(2'-hydroxy-5'-methylphenyl)-ben- zotriazole;
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole;
2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole;
2-(2'-hydroxy-5'-(1,1,3,- 3-tetramethylbutyl)phenyl)benzotriazole;
2-(3',5'-di-tert-butyl-2'-hydroxy- phenyl)-5-chlorobenzotriazole;
2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl-
)-5-chloro-benzotriazole;
2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)-- benzotriazole;
2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole;
2-(3',5'-di-tert-amyl-2'-hydroxphenyl)benzotriazole;
2-(3',5'-bis(.alpha.,.alpha.-dimethylbenzyl)-2'-hydroxyphenyl)-benzotriaz-
ole; a mixture of
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)-
phenyl)-5-chloro-benzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-c-
arbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-b-
enzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)pheny-
l)benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)p-
henyl)benzotriazole,
2-(3'tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-
-2'-hydroxyphenyl)benzotriazole,
2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)- benzotriazole and
2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonyleth-
yl)phenylbenzotriazole;
2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-be-
nzotriazol-2-ylphenol], the transesterification product of
2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]benzotriazo-
le with polyethylene glycol 300;
[R--CH.sub.2CH--COO(CH.sub.2).sub.3].sub.- 2 B where
R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl;
bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate;
bis(2,2,6,6-tetramethylp- iperidin-4-yl)succinate;
bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;
bis(1,2,2,6,6-pentamethylpiperidin-4-yl) n-butyl
3,5-di-tert-butyl-4-hydr- oxybenzylmalonate; the condensate of
1-(2-hydroxyethyl)-2,2,6,6-tetramethy- l-4-hydroxypiperidine and
succinic acid; the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-triazine;
tris(2,2,6,6-tetramethylpi- peridin-4-yl) nitrilotriacetate;
tetrakis(2,2,6,6-tetramethylpiperidin-4-y-
l)-1,2,3,4-butanetetracarboxylate;
1,1'-(1,2-ethanediyl)bis(3,3,5,5-tetram- ethylpiperazinone);
4-benzoyl-2,2,6,6-tetramethylpiperidine;
4-stearyloxy-2,2,6,6-tetramethylpiperidine;
bis(1,2,2,6,6-pentamethylpipe-
ridyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate;
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate; the
condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-morpholino-2,6-dichloro-1,3,5-triazine; the condensate of
2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triaz-
ine and 1,2-bis(3-aminopropylamino)ethane; the condensate of
2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-tri-
azine and 1,2-bis-(3- aminopropylamino)ethane;
8-acetyl-3-dodecyl-7,7,9,9--
tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione;
3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione;
3-dodecyl-1-(1-ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5--
dione;
3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidin-2,5-dio-
ne; a mixture of 4-hexadecyloxy- and
4-stearyloxy-2,2,6,6-tetramethylpiper- idine; the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexame- thylenediamine
and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; the condensate
of 1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-tr-
iazine and 4-butylamino-2,2,6,6-tetramethylpiperidine;
2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane;
oxo-piperanzinyl-triazines and the reaction product of
7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane
and epichlorohydrin;
2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazin- e;
2-(2-hydroxy-4-n-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-tria-
zine; 2-(2-hydroxy-4-(mixed
iso-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl- )-1,3,5-triazine;
2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,-
5-triazine;
2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,-
3,5-triazine;
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-
-triazine;
2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,-
3,5-triazine;
2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl-
)-1,3,5-triazine;
2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,-
6-bis(2,4-dimethylphenyl)-1,3,5-triazine;
2-[2-hydroxy-4-(2-hydroxy-3-octy-
loxypropyloxy)-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;
2-[4-dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,-
4-dimethylphenyl)-1,3,5-triazine;
2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypr-
opoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;
2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine;
2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine;
2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine;
2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,
2,4-dihydroxybenzophenone; 2-hydroxy-4-methoxybenzophenone;
2-hydroxy-4-octyloxybenzophenone; 2-hydroxy-4-decyloxybenzophenone;
2-hydroxy-4-dodecyloxybenzophenone;
2-hydroxy-4-benzyloxybenzophenone, 4,2',4-trishydroxybenzophenone;
2'-hydroxy-4,4'-dimethoxybenzophenone;
1,3,5-tris(2,6-dimethyl-4-tert-butyl-3hydroxybenzyl)isocyanurate;
1,3,5tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate; 1,3,5-
tris(3,5- di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene;
2,6-di-tert-butyl-4-methylphenol;
2,2'-ethylidene-bis(4,6-di-tert-butylph- enol);
1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane; esters of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono-
or polyhydric alcohols; esters of
.beta.-(5-tert-butyl-4-hydroxy-3-methylphe- nyl)propionic acid with
mono- or polyhydric alcohols;
dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate;
diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate;
dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate;
dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate; and
the calcium salt of the monoethyl ester of
3,5-di-tert-butyl-4-hydroxybenzylp- hosphonic acid; amides of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propio- nic acid such as
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexam-
ethylenediamine;
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trime-
thylenediamine; and
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hy-
drazine.
4. The composition of claim 3 wherein said compound of Formula I
has the formula: 51
5. The composition of claim 4 wherein R.sup.1 to R.sup.4 are
hydrogen, X is hydrogen, and L is hydrogen or a hydrocarbyl of 1 to
24 carbon atoms.
6. The composition of claim 3 wherein said compound of Formula I
has the formula 52
7. The composition of claim 6 wherein R3, R4 and X are hydrogen,
and L is hydrogen or a hydrocarbyl of 1 to 24 carbon atoms.
8. The composition of claim 1 further comprising a material to be
stabilized selected from the group consisting of: polyolefins,
polyesters, polyethers, polyketones, polyamides, natural and
synthetic rubbers, polyurethanes, polystyrenes, high-impact
polystyrenes, polyacrylates, polymethacrylates, polyacetals,
polyacrylonitriles, polybutadienes, polystyrenes, ABS, styrene
acrylonitrile, acrylate styrene acrylonitrile, cellulosic acetate
butyrate, cellulosic polymers, polyimides, polyamideimides,
polyetherimides, polyphenylsulfides, polyphenylene oxide,
polysulfones, polyethersulfones, polyvinylchlorides,
polycarbonates, polyketones, aliphatic polyketones, thermoplastic
TPO's, aminoresin crosslinked polyacrylates and polyesters,
polyisocyanate crosslinked polyesters and polyacrylates,
phenol/formaldehyde, urea/formaldehyde and melamine/formaldehyde
resins, drying and non-drying alkyd resins, alkyd resins, polyester
resins, acrylate resins cross-linked with melamine resins, urea
resins, isocyanates, isocyanurates, carbamates, epoxy resins,
cross-linked epoxy resins derived from aliphatic, cycloaliphatic,
heterocyclic and aromatic glycidyl compounds, which are
cross-linked with anhydrides or amines, polysiloxanes, Michael
addition polymers, amines, blocked amines with activated
unsaturated and methylene compounds, ketimines with activated
unsaturated and methylene compounds, polyketimines in combination
with unsaturated acrylic polyacetoacetate resins, polyketimines in
combination with unsaturated acrylic resins, radiation curable
compositions, epoxymelamine resins, organic dyes, cosmetic
products, cellulose-based paper formulations, photographic film
paper, ink, and mixtures thereof.
9. The composition of claim 8, wherein said compound of Formula I
has the formula: 53wherein R.sup.1 to R.sup.4 are hydrogen, X is
hydrogen, and L is hydrogen or a hydrocarbyl of 1 to 24 carbon
atoms.
10. The composition of claim 8, wherein said compound of Formula I
has the formula: 54wherein R3, R4 and X are hydrogen, and L is
hydrogen or a hydrocarbyl of 1 to 24 carbon atoms.
11. A composition comprising (a) a compound of Formula VII
55wherein T, T', R.sup.1, R.sup.2, Y, Z, R.sup.3, R.sup.4 G, m, n,
and o are defined as in claim 1; r is 2 or 3; when r is 2, X' is
--CO--R.sup.16--CO--, --CO.sub.2--R.sup.16--CO.sub.2--,
--SO.sub.2--R.sup.16--SO.sub.2--, --CO--NH--R.sup.17--NH--CO--, a
polyoxyalkylene bridge member of formula
--CO--(CH.sub.2).sub.u--O--(CH.sub.2--(CH.sub.2).sub.u--O--).sub.mm--(CH.-
sub.2).sub.u--CO--, or --COC(R.sup.21
)HCH.sub.2NH(C.sub.nnH.sub.2nnO).sub-
.mC.sub.nnH.sub.2nn--NHCH.sub.2--C(R.sup.21)HCO--when r=3, X' is:
--(--CO.sub.2--R.sup.16)R.sup.19, --(--CONH--R.sup.16)R.sup.19,
--(--SO.sub.2--R.sup.16)R.sup.19; R.sup.16 is C.sub.2-C.sub.10
alkylene, C.sub.2-C.sub.10 oxaalkylene or C.sub.2-C.sub.10
dithiaalkylene, phenylene, naphthylene, diphenylene or
C.sub.2-C.sub.6 alkenylene; R.sup.17 is C.sub.2-C.sub.10 alkylene,
phenylene, naphthylene, methylenediphenylene or C.sub.7-C.sub.15
alkylphenylene; and R.sup.18 is C.sub.2-C.sub.10 alkylene or
C.sub.4-C.sub.20 alkylene which is interrupted by one or more
oxygen atoms; R.sup.19 is C.sub.3-C.sub.10alkanetriyl; and R.sup.20
is C.sub.4-C.sub.10alkanetetryl- ; and (b) at least one additive
selected from the group consisting of:
2-(2'-hydroxy-5'-methylphenyl)-benzotriazole;
2-(3',5'-di-tert-butyl-2'-h- ydroxyphenyl)benzotriazole;
2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazol- e;
2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole;
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole;
2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chloro-benzotriazole;
2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)-benzotriazole;
2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole;
2-(3',5'-di-tert-amyl-2'-hyd- roxphenyl)benzotriazole;
2-(3',5'-bis(.alpha.,.alpha.-dimethylbenzyl)-2'-h-
ydroxyphenyl)-benzotriazole; a mixture of
2-(3'-tert-butyl-2'-hydroxy-5'-(-
2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-
-5-chloro-benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonyl-
ethyl)phenyl)-5-chloro-benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-me-
thoxycarbonylethyl)phenyl)benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-
-octyloxycarbonylethyl)phenyl)benzotriazole,
2-(3'-tert-butyl-5'-[2-(2-eth-
ylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole,
2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole and
2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotri-
azole;
2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylph-
enol], the transesterification product of
2-[3'-tert-butyl-5'-(2-methoxyca-
rbonylethyl)-2'-hydroxyphenyl]benzotriazole with polyethylene
glycol 300; [R--CH.sub.2CH--COO(CH.sub.2).sub.3].sub.2 B where
R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl;
bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate;
bis(2,2,6,6-tetramethylp- iperidin-4-yl)succinate;
bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;
bis(1,2,2,6,6-pentamethylpiperidin-4-yl) n-butyl
3,5-di-tert-butyl-4-hydr- oxybenzylmalonate; the condensate of
1-(2-hydroxyethyl)-2,2,6,6-tetramethy- l-4-hydroxypiperidine and
succinic acid; the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-triazine;
tris(2,2,6,6-tetramethylpi- peridin-4-yl) nitrilotriacetate;
tetrakis(2,2,6,6-tetramethylpiperidin-4-y- l)-
1,2,3,4-butanetetracarboxylate;
1,1'-(1,2-ethanediyl)bis(3,3,5,5-tetra- methylpiperazinone);
4-benzoyl-2,2,6,6-tetramethylpiperidine;
4-stearyloxy-2,2,6,6-tetramethylpiperidine;
bis(1,2,2,6,6-pentamethylpipe-
ridyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate;
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate; the
condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-morpholino-2,6-dichloro-1,3,5-triazine; the condensate of
2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triaz-
ine and 1,2-bis(3-aminopropylamino)ethane; the condensate of
2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-tri-
azine and 1,2-bis-(3- aminopropylamino)ethane;
8-acetyl-3-dodecyl-7,7,9,9--
tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione;
3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione;
3-dodecyl-1-(1-ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5--
dione;
3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidin-2,5-dio-
ne; a mixture of 4-hexadecyloxy- and
4-stearyloxy-2,2,6,6-tetramethylpiper- idine; the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexame- thylenediamine
and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; the condensate
of 1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-tr-
iazine and 4-butylamino-2,2,6,6-tetramethylpiperidine;
2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane;
oxo-piperanzinyl-triazines and the reaction product of
7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane
and epichlorohydrin;
2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazin- e;
2-(2-hydroxy-4-n-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-tria-
zine; 2-(2-hydroxy-4-(mixed
iso-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl- )-1,3,5-triazine;
2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,-
5-triazine;
2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,-
3,5-triazine;
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-
-triazine;
2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,-
3,5-triazine;
2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl-
)-1,3,5-triazine;
2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,-
6-bis(2,4-dimethylphenyl)-1,3,5-triazine;
2-[2-hydroxy-4-(2-hydroxy-3-octy-
loxypropyloxy)-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;
2-[4-dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,-
4-dimethylphenyl)-1,3,5-triazine;
2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypr-
opoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;
2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine;
2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine;
2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine;
2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,
2,4-dihydroxybenzophenone; 2-hydroxy-4-methoxybenzophenone;
2-hydroxy-4-octyloxybenzophenone; 2-hydroxy-4-decyloxybenzophenone;
2-hydroxy-4-dodecyloxybenzophenone;
2-hydroxy-4-benzyloxybenzophenone; 4,2',4-trishydroxybenzophenone;
2'-hydroxy-4,4'-dimethoxybenzophenone; 1,3,5-tris(
2,6-dimethyl-4-tert-butyl-3hydroxybenzyl)isocyanurate;
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate; 1,3,5-
tris(3,5- di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene;
2,6-di-tert-butyl-4-methylphenol;
2,2'-ethylidene-bis(4,6-di-tert-butylph- enol);
1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane; esters of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono-
or polyhydric alcohols; esters of
.beta.-(5-tert-butyl-4-hydroxy-3-methylphe- nyl)propionic acid with
mono- or polyhydric alcohols;
dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate;
diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate;
dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate;
dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate; and
the calcium salt of the monoethyl ester of
3,5-di-tert-butyl-4-hydroxybenzylp- hosphonic acid; amides of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propio- nic acid such as
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexam-
ethylenediamine;
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trime-
thylenediamine; and
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hy-
drazine.
12. A composition comprising: (a) a compound of Formula VI
56wherein T, X, Z, R.sup.1, R.sup.2, R.sup.3, R.sup.4, G, m, n, and
o are defined as in claim 1; r is an integer between 2 and 4; when
r is 2, D is selected from the group consisting of C.sub.2-C.sub.16
alkyl, C.sub.4-C.sub.12 alkenyl, xylylene, C.sub.3-C.sub.20 alkyl
which is interrupted by one or more oxygen atoms,
hydroxy-substituted C.sub.3-C.sub.20 alkyl which is interrupted by
one or more oxygen atoms, --CH.sub.2CH(OH)CH.sub.2O
--R.sup.15--OCH.sub.2CH(OH)CH.sub.2,--CO--R.sup.16--CO--,
--CO--NH--R.sup.17--NH--CO--,
--(CH.sub.2).sub.s--COO--R.sup.18--OCO--(CH- .sub.2).sub.s--a
polyoxyalkylene bridge member of the formula XX
--CH.sub.2--CH(OH)--CH.sub.2--O--(CH.sub.2--(CH.sub.2).sub.u--O--).sub.mm-
--CH.sub.2--CH(OH)--CH.sub.2-- (XX), a polyoxyalkylene bridge
member of the formula XXI
--CO--(CH.sub.2).sub.u--O--(CH.sub.2--(CH.sub.2).sub.u--O-
--).sub.mm--(CH.sub.2).sub.u--CO-- (XXI), a polyoxyalkylene bridge
member of the formula XXII
--YY--O--CO(CH.sub.2).sub.u--O--(CH.sub.2--(CH.sub.2)-
.sub.u--O--).sub.mm--(CH.sub.2).sub.u--COO--YY-- (XXII), a
polyoxyalkylene bridge member of the formula XXIII
--(CH.sub.2).sub.kk--CH(R.sup.21)--CO--B.sub.1--(C.sub.nnH.sub.2nn--O--).-
sub.mmC.sub.nnH.sub.2nnB.sub.1--CO--CH(R.sup.21)--(CH.sub.2).sub.kk--
(XXIII), a polyoxyalkylene bridge member of the formula XXIV
--COC(R.sup.21)HCH.sub.2NH(C.sub.nnH.sub.2nnO).sub.mC.sub.nnH.sub.2nn--NH-
CH.sub.2--C(R.sup.21)HCO--a polyoxyalkylene bridge member of the
formula XXV
--YY--O--CO--(CH.sub.2).sub.2--NH--(C.sub.nnH.sub.2nn--O--).sub.mm--C-
.sub.nnH.sub.2nn--NH--(CH.sub.2).sub.2COO--YY-- (XXV), a
polyoxyalkylene bridge member of the formula XXVI
--(C.sub.nnH.sub.2nn--O--).sub.mm--C.su- b.nnH.sub.2nn-- (XXVI),
and a polyoxyalkylene bridge member of the formula XXVII
--CH(CH.sub.3)--CH.sub.2--(O--CH(CH.sub.3)--CH.sub.2).sub.a
--(O--CH.sub.2--CH.sub.2).sub.b--(O--CH--CH(CH.sub.3).sub.c--
(XXVII), wherein a+c=2.5 and b=8.5 to 40.5 or a+c=2 to 33 and b=0,
R.sup.21 is hydrogen or C.sub.1-C.sub.16 alkyl, R.sup.22 is halogen
or --O--R.sup.23, R.sup.23 is hydrogen, C.sub.1-C.sub.6 alkyl,
C.sub.3-C.sub.6 alkenyl, aryl, or aryl-C.sub.1-C.sub.4-alkyl,
R.sup.24 is hydrogen, C.sub.1-C.sub.12 alkyl or aryl, R.sup.25 is
C.sub.1-C.sub.16 alkyl, C.sub.5-C.sub.12 cycloalkyl,
C.sub.3-C.sub.6 alkenyl, C.sub.1-C.sub.12 alkylaryl or
aryl-C.sub.1-C.sub.4 alkyl, R.sup.26 is hydrogen or C.sub.1-C.sub.4
alkyl, R.sup.27 is hydrogen, C.sub.1-C.sub.18 alkyl,
C.sub.3-C.sub.6 alkenyl, C.sub.1-C.sub.18 alkoxy, halogen or
aryl-C.sub.1-C.sub.4 alkyl, R.sup.28 and R.sup.29 independently of
one another are hydrogen, C.sub.1-C.sub.18 alkyl, C.sub.3-C.sub.6
alkenyl, or C.sub.1-C.sub.18 alkoxy, or halogen; R.sup.30 is
hydrogen, C.sub.1-C.sub.4 alkyl or CN, YY is unsubstituted or
substituted C.sub.2-C.sub.20 alkyl, kk is zero or an integer from
1-16, B.sub.1 is O or NH, mm is an integer from 2 to 60, nn is an
integer from 2 to 6, u is an integer from 1 to 4; when r is 3, D is
(CH.sub.2).sub.s--COO.sub.3--R.- sup.19 and when r is 4, D is
(CH.sub.2).sub.s--COO.sub.4--R.sup.20 wherein R.sup.19 is
C.sub.3-C.sub.10 alkanetriyl and R.sup.20 is C.sub.4-C.sub.10
alkanetetryl; and s is 1-6; R.sup.15 is C.sub.2-C.sub.10 alkyl,
C.sub.2-C.sub.10 oxaalkyl or C.sub.2-C.sub.10 dithiaalkyl, phenyl,
naphthyl, diphenyl, or C.sub.2-C.sub.6 alkenyl, or
phenylene-XX-phenylene wherein XX is --O--, --S--, --SO.sub.2--,
--CH.sub.2--, or --C(CH.sub.3).sub.2--; R.sup.16 is
C.sub.2-C.sub.10 alkyl, C.sub.2-C.sub.10 oxaalkyl or
C.sub.2-C.sub.10 dithiaalkyl, phenyl, naphthyl, diphenyl, or
C.sub.2-C.sub.6 alkenyl provided that when r is 3 the alkenyl has
at least 3 carbons; R.sup.17 is C.sub.2-C.sub.10 alkyl, phenyl,
naphthyl, diphenyl, or C.sub.2-C.sub.6 alkenyl,
methylenediphenylene, or C.sub.4-C.sub.15 alkylphenyl; and R.sup.18
is C.sub.2-C.sub.10 alkyl, or C.sub.4-C.sub.20 alkyl interrupted by
one or more oxygen atoms; and (b) at least one additive selected
from the group consisting of:
2-(2'-hydroxy-5'-methylphenyl)-benzotriazole;
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole;
2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole;
2-(2'-hydroxy-5'-(1,1,3,- 3-tetramethylbutyl)phenyl)benzotriazole;
2-(3',5'-di-tert-butyl-2'-hydroxy- phenyl)-5-chlorobenzotriazole;
2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl-
)-5-chloro-benzotriazole;
2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)-- benzotriazole;
2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole;
2-(3',5'-di-tert-amyl-2'-hydroxphenyl)benzotriazole;
2-(3',5'-bis(.alpha.,.alpha.-dimethylbenzyl)-2'-hydroxyphenyl)-benzotriaz-
ole; a mixture of
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)-
phenyl)-5-chloro-benzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-c-
arbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-b-
enzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)pheny-
l)benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)p-
henyl)benzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl-
]-2'-hydroxyphenyl)benzotriazole,
2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl- )benzotriazole and
2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylet-
hyl)phenylbenzotriazole;
2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-b-
enzotriazol-2-ylphenol], the transesterification product of
2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]benzotriazo-
le with polyethylene glycol 300;
[R--CH.sub.2CH--COO(CH.sub.2).sub.3].sub.- 2 B where
R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl;
bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate;
bis(2,2,6,6-tetramethylp- iperidin-4-yl)succinate;
bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;
bis(1,2,2,6,6-pentamethylpiperidin-4-yl) n-butyl
3,5-di-tert-butyl-4-hydr- oxybenzylmalonate; the condensate of
1-(2-hydroxyethyl)-2,2,6,6-tetramethy- l-4-hydroxypiperidine and
succinic acid; the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-triazine;
tris(2,2,6,6-tetramethylpi- peridin-4-yl) nitrilotriacetate;
tetrakis(2,2,6,6-tetramethylpiperidin-4-y-
l)-1,2,3,4-butanetetracarboxylate;
1,1'-(1,2-ethanediyl)bis(3,3,5,5-tetram- ethylpiperazinone);
4-benzoyl-2,2,6,6-tetramethylpiperidine;
4-stearyloxy-2,2,6,6-tetramethylpiperidine;
bis(1,2,2,6,6-pentamethylpipe-
ridyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate;
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate; the
condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-morpholino-2,6-dichloro-1,3,5-triazine; the condensate of
2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triaz-
ine and 1,2-bis(3-aminopropylamino)ethane; the condensate of
2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-tri-
azine and 1,2-bis-(3-aminopropylamino)ethane;
8-acetyl-3-dodecyl-7,7,9,9-t-
etramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione;
3-dodecyl-1-(2,2,6,6-te-
tramethylpiperidin-4-yl)pyrrolidin-2,5-dione;
3-dodecyl-1-(1-ethanoyl-2,2,-
6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione;
3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione;
a mixture of 4-hexadecyloxy- and
4-stearyloxy-2,2,6,6-tetramethylpiperidine- ; the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethyle- nediamine
and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; the condensate
of 1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-tr-
iazine and 4-butylamino-2,2,6,6-tetramethylpiperidine;
2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane;
oxo-piperanzinyl-triazines and the reaction product of
7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane
and epichlorohydrin;
2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazin- e;
2-(2-hydroxy-4-n-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-tria-
zine; 2-(2-hydroxy-4-(mixed
iso-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl- )-1,3,5-triazine;
2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,-
5-triazine;
2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,-
3,5-triazine;
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-
-triazine;
2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,-
3,5-triazine;
2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl-
)-1,3,5-triazine;
2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,-
6-bis(2,4-dimethylphenyl)-1,3,5-triazine;
2-[2-hydroxy-4-(2-hydroxy-3-octy-
loxypropyloxy)-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;
2-[4-dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,-
4-dimethylphenyl)-1,3,5-triazine;
2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypr-
opoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;
2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine;
2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine;
2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine;
2-(2-hydroxyphenyl)4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,
2,4-dihydroxybenzophenone; 2-hydroxy-4-methoxybenzophenone;
2-hydroxy-4-octyloxybenzophenone; 2-hydroxy-4-decyloxybenzophenone;
2-hydroxy-4-dodecyloxybenzophenone;
2-hydroxy-4-benzyloxybenzophenone, 4,2',4-trishydroxybenzophenone;
2'-hydroxy-4,4'-dimethoxybenzophenone; 1,3,5-tris(
2,6-dimethyl-4-tert-butyl-3hydroxybenzyl)isocyanurate;
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate; 1,3,5-
tris(3,5- di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene;
2,6-di-tert-butyl-4-methylphenol;
2,2'-ethylidene-bis(4,6-di-tert-butylph- enol);
1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane; esters of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono-
or polyhydric alcohols; esters of
.beta.-(5-tert-butyl-4-hydroxy-3-methylphe- nyl)propionic acid with
mono- or polyhydric alcohols;
dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate;
diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate;
dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate;
dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate; and
the calcium salt of the monoethyl ester of
3,5-di-tert-butyl-4-hydroxybenzylp- hosphonic acid; amides of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propio- nic acid such as
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexam-
ethylenediamine;
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trime-
thylenediamine; and
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hy-
drazine.
13. A composition comprising: (a) a compound of Formula IX
57wherein A, T, T', X, Y, R.sup.1, R.sup.2, R.sup.3, R.sup.4, G, m,
n and o, are defined as in claim 1; r is an integer between 2 and
4; when r is 2, D is selected from the group consisting of
C.sub.2-C.sub.16 alkylene, C.sub.4-C.sub.12 alkenylene, xylylene,
C.sub.3-C.sub.20 alkylene which is interrupted by one or more
oxygen atoms, hydroxy-substituted C.sub.3-C.sub.20 alkylene which
is interrupted by one or more oxygen atoms, --OOCR.sup.14COO--,
--CH.sub.2CH(OH)CH.sub.2O--R.sup.15--OCH.sub.2- CH(OH)CH.sub.2,
--CO--R.sup.16--CO--, --CO--NH--R.sup.17--NH--CO--, and
--(CH.sub.2).sub.s--COO--R.sup.18--OCO--(CH.sub.2).sub.s--; and
when r is 3, D is (CH.sub.2).sub.s--COO.sub.3--R.sup.19 and when r
is 4, D is (CH.sub.2).sub.s--COO.sub.4--R.sup.20 wherein R.sup.19
is C.sub.3-C.sub.10 alkanetriyl and R.sup.20 is C.sub.4-C.sub.10
alkanetetryl; s is 1-6; r is an integer between 2 and 4; when r is
2, D is selected from the group consisting of C.sub.2-C.sub.16
alkylene, C.sub.4-C.sub.12 alkenylene, xylylene, C.sub.3-C.sub.20
alkylene which is interrupted by one or more oxygen atoms,
hydroxy-substituted C.sub.3-C.sub.20 alkylene which is interrupted
by one or more oxygen atoms,
--CH.sub.2CH(OH)CH.sub.2O--R.sup.15--OCH.sub.2CH(OH)CH.sub.2,
--CO--R.sup.16--CO--, --CO--NH--R.sup.17--NH--CO--, and
--(CH.sub.2).sub.s--COO--R.sup.18--OCO--(CH.sub.2).sub.s--; and
when r is 3, D is (CH.sub.2).sub.s--COO.sub.3--R.sup.19 and when r
is 4, D is (CH.sub.2).sub.s--COO.sub.4--R.sup.20 wherein R.sup.19
is C.sub.3-C.sub.10 alkanetriyl and R.sup.20 is C.sub.4-C.sub.10
alkanetetryl; s is 1-6; R.sup.8 is C.sub.1-C.sub.18 alkyl,
C.sub.3-C.sub.18 alkenyl, C.sub.3-C.sub.20 alkyl, which is
interrupted by O, N, or S, and/or substituted by OH,
C.sub.1-C.sub.4 alkyl which is substituted by
--P(O)(OR.sup.14).sub.2, --N(R.sup.9) (R.sup.10), or --OCOR.sup.11,
and/or OH, or is glycidyl, cyclohexyl or C.sub.7-C.sub.11
phenylalkyl; R.sup.9 and R.sup.10 are each independently of the
other, C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 alkoxyalkyl,
C.sub.4-C.sub.16 dialkylaminoalkyl or C.sub.5-C.sub.12 cycloalkyl,
or R.sup.9 and R.sup.10, when taken together, are C.sub.3-C.sub.9
alkylene or C.sub.3-C.sub.9 oxaalkylene of C.sub.3-C.sub.9
azaalkylene; R.sup.11 is C.sub.1-C.sub.18 alkyl, C.sub.2-C.sub.18
alkenyl or phenyl; R.sup.12 is C.sub.1-C.sub.18 alkyl,
C.sub.2-C.sub.18 alkenyl, phenyl, C.sub.1-C.sub.12 alkoxy, phenoxy,
C.sub.1-C.sub.12 alkylamino; phenylamino, tolylamino or
naphthylamino; R.sup.13 is C.sub.1-C.sub.12 alkyl, phenyl, naphthyl
or C.sub.7-C.sub.14 alkylphenyl; R.sup.14 is C.sub.1-C.sub.12 alkyl
or phenyl; R.sup.15 is C.sub.2-C.sub.10 alkylene phenylene or a
phenylene-x-phenylene- group, wherein X is --O--, --S--,
--SO.sub.2--, --CH.sub.2--, or --C(CH.sub.3).sub.2--; R.sup.16 is
C.sub.2-C.sub.10 alkylene, C.sub.2-C.sub.10 oxaalkylene or
C.sub.2-C.sub.10 dithiaalkylene, phenylene, naphthylene,
diphenylene or C.sub.2-C.sub.6 alkenylene; R.sup.17 is
C.sub.2-C.sub.10 alkylene, phenylene, naphthylene,
methylenediphenylene or C.sub.7-C.sub.15 alkylphenylene, and
R.sup.18 is C.sub.2-C.sub.10 alkylene or C.sub.4-C.sub.20 alkylene
which is interrupted by one or more oxygen atoms; and (b) at least
one additive selected from the group consisting of:
2-(2'-hydroxy-5'-methylphenyl)-benzotriazole;
2-(3',5'-di-tert-butyl-- 2'-hydroxyphenyl)benzotriazole;
2-(5'-tert-butyl-2'-hydroxyphenyl)benzotri- azole;
2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole;
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole;
2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chloro-benzotriazole;
2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)-benzotriazole;
2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole;
2-(3',5'-di-tert-amyl-2'-hyd- roxphenyl)benzotriazole;
2-(3',5'-bis(.alpha.,.alpha.-dimethylbenzyl)-2'-h-
ydroxyphenyl)-benzotriazole; a mixture of
2-(3'-tert-butyl-2'-hydroxy-5'-(-
2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-
-5-chloro-benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonyl-
ethyl)phenyl)-5-chloro-benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-me-
thoxycarbonylethyl)phenyl)benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-
-octyloxycarbonylethyl)phenyl)benzotriazole,
2-(3'-tert-butyl-5'-[2-(2-eth-
ylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole,
2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole and
2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotri-
azole;
2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylph-
enol], the transesterification product of
2-[3'-tert-butyl-5'-(2-methoxyca-
rbonylethyl)-2'-hydroxyphenyl]benzotriazole with polyethylene
glycol 300; [R--CH.sub.2CH--COO(CH.sub.2).sub.3].sub.2 B where
R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl;
bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate;
bis(2,2,6,6-tetramethylp- iperidin-4-yl)succinate;
bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;
bis(1,2,2,6,6-pentamethylpiperidin-4-yl) n-butyl
3,5-di-tert-butyl-4-hydr- oxybenzylmalonate; the condensate of
1-(2-hydroxyethyl)-2,2,6,6-tetramethy- l-4-hydroxypiperidine and
succinic acid; the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-triazine;
tris(2,2,6,6-tetramethylpi- peridin-4-yl) nitrilotriacetate;
tetrakis(2,2,6,6-tetramethylpiperidin-4-y- l)-
1,2,3,4-butanetetracarboxylate;
1,1'-(1,2-ethanediyl)bis(3,3,5,5-tetra- methylpiperazinone);
4-benzoyl-2,2,6,6-tetramethylpiperidine;
4-stearyloxy-2,2,6,6-tetramethylpiperidine;
bis(1,2,2,6,6-pentamethylpipe-
ridyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate;
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate; the
condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-morpholino-2,6-dichloro-1,3,5-triazine; the condensate of
2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triaz-
ine and 1,2-bis(3-aminopropylamino)ethane; the condensate of
2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-tri-
azine and 1,2-bis-(3- aminopropylamino)ethane;
8-acetyl-3-dodecyl-7,7,9,9--
tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione;
3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione;
3-dodecyl-1-(1-ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5--
dione;
3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-di-
one; a mixture of 4-hexadecyloxy- and
4-stearyloxy-2,2,6,6-tetramethylpipe- ridine; the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexam- ethylenediamine
and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; the condensate
of 1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-tr-
iazine and 4-butylamino-2,2,6,6-tetramethylpiperidine;
2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane;
oxo-piperanzinyl-triazines and the reaction product of
7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane
and epichlorohydrin;
2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazin- e;
2-(2-hydroxy-4-n-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-tria-
zine; 2-(2-hydroxy-4-(mixed
iso-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl- )-1,3,5-triazine;
2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,-
5-triazine;
2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,-
3,5-triazine;
2-(2-hydroxy4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5--
triazine;
2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3-
,5-triazine;
2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-
-1,3,5-triazine;
2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,6-
-bis(2,4-dimethylphenyl)-1,3,5-triazine;
2-[2-hydroxy-4-(2-hydroxy-3-octyl-
oxypropyloxy)-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;
2-[4-dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,-
4-dimethylphenyl)-1,3,5-triazine;
2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypr-
opoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;
2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine;
2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine;
2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine;
2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,
2,4-dihydroxybenzophenone; 2-hydroxy-4-methoxybenzophenone;
2-hydroxy-4-octyloxybenzophenone; 2-hydroxy-4-decyloxybenzophenone;
2-hydroxy-4-dodecyloxybenzophenone;
2-hydroxy-4-benzyloxybenzophenone, 4,2',4-trishydroxybenzophenone
2'-hydroxy4,4'-dimethoxybenzophenone; 1,3,5-tris(
2,6-dimethyl-4-tert-butyl-3hydroxybenzyl)isocyanurate;
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate; 1,3,5-
tris(3,5- di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene;
2,6-di-tert-butyl-4-methylphenol;
2,2'ethylidene-bis(4,6-di-tert-butylphe- nol);
1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane; esters of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono-
or polyhydric alcohols; esters of
.beta.-(5-tert-butyl-4-hydroxy-3-methylphe- nyl)propionic acid with
mono- or polyhydric alcohols;
dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate;
diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate;
dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate;
dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate; and
the calcium salt of the monoethyl ester of
3,5-di-tert-butyl-4-hydroxybenzylp- hosphonic acid; amides of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propio- nic acid such as
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexam-
ethylenediamine;
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trime-
thylenediamine; and
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hy-
drazine.
14. A composition comprising (a) a compound of Formula I 58wherein
T is a direct bond, carbon, oxygen, nitrogen, sulfur or a
functional group containing these elements; T' is oxygen, nitrogen,
sulfur or carbon; X is independently selected from hydrogen and a
blocking group; each of R.sup.1 and R.sup.2 independently a
hydrocarbyl group, a functional hydrocarbyl group, hydroxy, alkoxy,
hydrogen, halogen, cyano, or isocyano, wherein the hydrocarbyl has
1 to 24 arbon atoms; each of Y, R.sup.3 and R .sup.4are
independently a hydrogen, hydrocarbyl group, a functional
hydrocarbyl group, halogen, hydroxyl, cyano, --O(hydrocarbyl),
--O(functional hydrocarbyl), --N(hydrocarbyl).sub.2, --N(functional
hydrocarbyl).sub.2, --N(hydrocarbyl)(functional hydrocarbyl),
--S(hydrocarbyl), --S(functional hydrocarbyl),
--SO.sub.2(hydrocarbyl), --SO.sub.2(functional hydrocarbyl),
--SO.sub.3(hydrocarbyl), --SO.sub.3(functional hydrocarbyl),
--CO.sub.2(hydrocarbyl), --CO.sub.2(functional hydrocarbyl),
--CO(hydrocarbyl), --CO(functional hydrocarbyl),
--OCO(hydrocarbyl), --OCO(functional hydrocarbyl), --CONH.sub.2,
--CONH(hyrdocarbyl), --CONH(functional hyrdocarbyl),
--CON(hydrocarbyl).sub.2, --CON(hydrocarbyl)(functional
hyrdocarbyl), --CON(functional hydrocarbyl).sub.2, wherein the
hydrocarbyl or functional hydrocarbyl may be the same or different
and has 1 to 24 carbon atoms; Z is Y, 59wherein L is hydrogen, a
hydrocarbyl group of 1 to 24 carbon atoms, or a functional
hydrocarbyl group of 1 to 24 carbon atoms; X is independently
selected from hydrogen and a blocking group; and R.sup.3 and
R.sup.4 are independently hydrogen, hydrocarbyl, functional
hydrocarbyl, halogen, hydroxyl, --O(hydrocarbyl), --O(functional
hydrocarbyl), --S(hydrocarbyl), --SO.sub.2(hydrocarbyl),
--SO.sub.3(hydrocarbyl), --CO.sub.2(hydrocarbyl),
--CO(hydrocarbyl), --OCO(hydrocarbyl), --N(hydrocarbyl).sub.2,
--S(functional hydrocarbyl), --SO.sub.2(functional hydrocarbyl),
-SO.sub.3(functional hydrocarbyl), --CO.sub.2(functional
hydrocarbyl), --CO(functional hydrocarbyl), --OCO(functional
hydrocarbyl), --N(functional hydrocarbyl).sub.2 or cyano wherein
the hydrocarbyl or functional hydrocarbyl may be the same or
different and has 1 to 24 carbon atoms; each G is independently a
direct bond, nitrogen, sulfur, oxygen, or functional groups
containing these elements; each of m, n, and o is independently an
integer between 0 and 4, provided that when both G are direct
bonds, the sum of m, n and o is between 2 and 10, and that when one
G is a direct bond, the sum of m, n and o is between 1 and 9, and
when neither G is a direct bond, the sum of m, n and o is between 0
and 8; and (b) a material to be stabilized selected from the group
consisting of: polyolefins, polyesters, polyethers, polyketones,
polyamides, natural and synthetic rubbers, polyurethanes,
polystyrenes, high-impact polystyrenes, polyacrylates,
polymethacrylates, polyacetals, polyacrylonitriles, polybutadienes,
polystyrenes, ABS, styrene acrylonitrile, acrylate styrene
acrylonitrile, cellulosic acetate butyrate, cellulosic polymers,
polyimides, polyamideimides, polyetherimides, polyphenylsulfides,
polyphenylene oxide, polysulfones,
polyethersulfones,-polyvinylchlorides, polycarbonates, polyketones,
aliphatic polyketones, thermoplastic TOP's, aminoresin crosslinked
polyacrylates and polyesters, polyisocyanate crosslinked polyesters
and polyacrylates, phenol/formaldehyde, urea/formaldehyde and
melamine/formaldehyde resins, drying and non-drying alkyd resins,
alkyd resins, polyester resins, acrylate resins cross-linked with
melamine resins, urea resins, isocyanates, isocyanurates,
carbamates, epoxy resins, cross-linked epoxy resins derived from
aliphatic, cycloaliphatic, heterocyclic and aromatic glycidyl
compounds, which are cross-linked with anhydrides or amines,
polysiloxanes, Michael addition polymers, amines, blocked amines
with activated unsaturated and methylene compounds, ketimines with
activated unsaturated and methylene compounds, polyketimines in
combination with unsaturated acrylic polyacetoacetate resins,
polyketimines in combination with unsaturated acrylic resins,
radiation curable compositions, epoxymelamine resins, organic dyes,
cosmetic products, cellulose-based paper formulations, photographic
film paper, ink, and mixtures thereof.
15. A composition of claim 14, wherein said compound of formula 1
has the formula: 60wherein R.sup.3, R.sup.4 and X are hydrogen, and
L is hydrogen or a hydrocarbyl of 1 to 24 carbon atoms.
16. A composition comprising: (a) a compound of Formula VI
61wherein T, X, Z, R.sup.1, R.sup.2, R.sup.3, R.sup.4, G, m, n, and
o are defined as in claim 1; r is an integer between 2 and 4; when
r is 2, D is selected from the group consisting of C.sub.2-C.sub.16
alkyl, C.sub.4-C.sub.12 alkenyl, xylylene, C.sub.3-C.sub.20 alkyl
which is interrupted by one or more oxygen atoms,
hydroxy-substituted C.sub.3-C.sub.20 alkyl which is interrupted by
one or more oxygen atoms, --CH.sub.2CH(OH)CH.sub.2O--R.sup-
.15--OCH.sub.2CH(OH)CH.sub.2, --CO--R.sup.16--CO--,
--CO--NH--R.sup.17--NH--CO--,
--(CH.sub.2).sub.s--COO--R.sup.18--OCO--(CH- .sub.2).sub.s--a
polyoxyalkylene bridge member of the formula XX
--CH.sub.2--CH(OH)--CH.sub.2--O--(CH.sub.2--(CH.sub.2).sub.u--O--).sub.mm-
--CH.sub.2--CH(OH)--CH.sub.2-- (XX), a polyoxyalkylene bridge
member of the formula XXI
--CO--(CH.sub.2).sub.u--O--(CH.sub.2--(CH.sub.2).sub.u--O-
--).sub.mm--(CH.sub.2).sub.u--CO-- (XXI), a polyoxyalkylene bridge
member of the formula XXII
--YY--O--CO(CH.sub.2).sub.u--O--(CH.sub.2--(CH.sub.2)-
--O--).sub.mm--(CH.sub.2).sub.u--COO--Y-- (XXII), a polyoxyalkylene
bridge member of the formula XXIII
--(CH.sub.2).sub.kk--CH(R.sup.21)--CO--
-B.sub.1--(C.sub.nnH.sub.2nn--O--).sub.mmC.sub.nnH.sub.2nn--B--CO--CH(R.su-
p.21)--(CH.sub.2).sub.kk-- (XXIII), a polyoxyalkylene bridge member
of the formula XXIV --COC(R.sup.21
)HCH.sub.2NH(C.sub.nnH.sub.2nnO).sub.mC.s-
ub.nnH.sub.2nn--NHCH.sub.2--C(R.sup.21 )HCO--a polyoxyalkylene
bridge member of the formula XXV
--YY--O--CO--(CH.sub.2).sub.2--NH--(C.sub.nnH.s-
ub.2nn--O--).sub.mm--C.sub.nnH.sub.2nn--NH--(CH.sub.2).sub.2COO--YY--
(XXV), a polyoxyalkylene bridge member of the formula XXVI
--(C.sub.nnH.sub.2nn--O--).sub.mm--C.sub.nnH.sub.2nn-- (XXVI), and
a polyoxyalkylene bridge member of the formula XXVII
--CH(CH.sub.3)--CH.sub.2--(O--CH(CH.sub.3)--CH.sub.2).sub.a--(O--CH.sub.2-
--CH.sub.2).sub.b--(O--CH.sub.2--CH(CH.sub.3).sub.c-- (XXVII),
wherein a+c=2.5 and b=8.5to 40.5 or a+c=2 to 33 and b=0, R.sup.21
is hydrogen or C.sub.1-C.sub.16 alkyl, R.sup.22 is halogen or
--O--R.sup.23, R.sup.23 is hydrogen, C.sub.1-C.sub.6 alkyl,
C.sub.3-C.sub.6 alkenyl, aryl, or aryl-C.sub.1-C.sub.4-alkyl,
R.sup.24 is hydrogen, C.sub.1-C.sub.12 alkyl or aryl, R.sup.25 is
C.sub.1-C.sub.16 alkyl, C.sub.5-C.sub.12 cycloalkyl,
C.sub.3-C.sub.6 alkenyl, C.sub.1-C.sub.12 alkylaryl or
aryl-C.sub.1-C.sub.4 alkyl, R.sup.26 is hydrogen or C.sub.1-C.sub.4
alkyl, R.sup.27 is hydrogen, C.sub.1-C.sub.18 alkyl,
C.sub.3-C.sub.6 alkenyl, C.sub.1-C.sub.18 alkoxy, halogen or
aryl-C.sub.1-C.sub.4 alkyl, R.sup.28 and R.sup.29 independently of
one another are hydrogen, C.sub.1-C.sub.18 alkyl, C.sub.3-C.sub.6
alkenyl, or C.sub.1-C.sub.8 alkoxy, or halogen; R.sup.30 is
hydrogen, C.sub.1-C.sub.4 alkyl or CN, YY is unsubstituted or
substituted C.sub.2-C.sub.20 alkyl, kk is zero or an integer from
1-16, B.sub.1 is O or NH, mm is an integer from 2 to 60, nn is an
integer from 2 to 6, u is an integer from 1 to 4; when r is 3, D is
(CH.sub.2).sub.s--COO.sub.3--R.sup.19 and when r is 4, D is
(CH.sub.2).sub.s--COO.sub.4--R.sup.20 wherein R.sup.19 is
C.sub.3-C.sub.10 alkanetriyl and R.sup.20 is C.sub.4-C.sub.10
alkanetetryl; and s is 1-6; R.sup.15 is C.sub.2-C.sub.10 alkyl,
C.sub.2-C.sub.10 oxaalkyl or C.sub.2-C.sub.10 dithiaalkyl, phenyl,
naphthyl, diphenyl, or C.sub.2-C.sub.6 alkenyl, or
phenylene-XX-phenylene wherein XX is --O--, --S--, --SO.sub.2--,
--CH.sub.2--, or --C(CH.sub.3).sub.2--; R.sup.16 is
C.sub.2-C.sub.10 alkyl, C.sub.2-C.sub.10 oxaalkyl or
C.sub.2-C.sub.10 dithiaalkyl, phenyl, naphthyl, diphenyl, or
C.sub.2-C.sub.6 alkenyl provided that when r is 3 the alkenyl has
at least 3 carbons; R.sup.17 is C.sub.2-C.sub.10 alkyl, phenyl,
naphthyl, diphenyl, or C.sub.2-C.sub.6 alkenyl,
methylenediphenylene, or C.sub.4-C.sub.15 alkylphenyl; and R.sup.18
is C.sub.2-C.sub.10 alkyl, or C.sub.4-C.sub.20 alkyl interrupted by
one or more oxygen atoms; and (b) a material to be stabilized
selected from the group consisting of: polyolefins, polyesters,
polyethers, polyketones, polyamides, natural and synthetic rubbers,
polyurethanes, polystyrenes, high-impact polystyrenes,
polyacrylates, polymethacrylates, polyacetals, polyacrylonitriles,
polybutadienes, polystyrenes, ABS, styrene acrylonitrile, acrylate
styrene acrylonitrile, cellulosic acetate butyrate, cellulosic
polymers, polyimides, polyamideimides, polyetherimides,
polyphenylsulfides, polyphenylene oxide, polysulfones,
polyethersulfones, polyvinylchlorides, polycarbonates, polyketones,
aliphatic polyketones, thermoplastic TOP's, aminoresin crosslinked
polyacrylates and polyesters, polyisocyanate crosslinked polyesters
and polyacrylates, phenol/formaldehyde, urea/formaldehyde and
melamine/formaldehyde resins, drying and non-drying alkyd resins,
alkyd resins, polyester resins, acrylate resins cross-linked with
melamine resins, urea resins, isocyanates, isocyanurates,
carbamates, epoxy resins, cross-linked epoxy resins derived from
aliphatic, cycloaliphatic, heterocyclic and aromatic glycidyl
compounds, which are cross-linked with anhydrides or amines,
polysiloxanes, Michael addition polymers, amines, blocked amines
with activated unsaturated and methylene compounds, ketimines with
activated unsaturated and methylene compounds, polyketimines in
combination with unsaturated acrylic polyacetoacetate resins,
polyketimines in combination with unsaturated acrylic resins,
radiation curable compositions, epoxymelamine resins, organic dyes,
cosmetic products, cellulose-based paper formulations, photographic
film paper, ink, and mixtures thereof.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention relates generally to novel
benzocycle-substituted pyrimidines and triazines and their use as
protectants against degradation by environmental forces, including
ultraviolet light, actinic radiation, oxygen, moisture, atmospheric
pollutants and combinations thereof.
[0003] 2. Description of Related Art
[0004] Exposure to sunlight and other sources of ultraviolet
radiation is known to cause degradation of a variety of materials,
especially polymeric materials. For example, polymeric materials
such as plastics often discolor and may become brittle as a result
of exposure to ultraviolet light. Accordingly, a large body of art
has been developed directed towards materials such as ultraviolet
light absorbers and stabilizers which are capable of inhibiting
such degradation.
[0005] A class of materials known to be ultraviolet light absorbers
are o-hydroxyphenyltriazines, in which at least one substituent on
the 1, 3 or 5 carbon on the triazine ring is a phenyl group with a
hydroxyl group ortho to the point of attachment to the triazine
ring. In general this class of materials is well known in the
art.
[0006] For example, U.S. Pat. No. 3,843,371 discloses
hydroxyphenyltriazines for use in photographic materials. The
triazines in this patent, however, show poor solubilities and poor
stabilities.
[0007] U.S. Pat. No. 3,896,125 discloses hydroxyphenyl triazines,
but these, too are poorly soluble and discolor with time.
[0008] The use of hydroxyphenyltriazines alone or in combination
with other light stabilizers such as hydroxyphenylbenzotriazoles,
benzophenones, oxanilides, cyanoacrylates, salicylates, and
hindered amine light stabilizers (HALS), for the stabilization of
polymers is also well known. For example, U.S. Pat. Nos. 4,853,471,
4,921,966, and 4,973,701, 4,973,702 disclose such combinations.
[0009] Typically, the aforementioned aryl ring with the hydroxyl
group ortho to the point of attachment to the triazine ring is
based on resorcinol and, consequently, this aryl ring also contains
a second substituent (either a hydroxyl group or a derivative
thereof) para- to the point of attachment to the triazine ring. For
example, U.S. Pat. No. 3,118,837 and 3,244,708 disclose
p-alkoxy-o-hydroxyphenyl triazines with improved UV protection, but
many embodiments of such triazines exhibit poor compatibility and
solubility, and poor yellowing performance.
[0010] This para- substituent can be "non-reactive," as in the case
of an alkyloxy group, or "reactive" as in the case of a
hydroxyalkyloxy (active hydrogen reactive site) or (meth)acryloyl
(ethylenic unsaturation reactive site) group. For the purposes of
the present invention, the former are referred to as "non-bondable"
benzocycle-substituted pyrimidines and triazines and the latter are
referred to as "bondable" benzocycle-substituted pyrimidines and
triazines.
[0011] Low volatility is an important characteristic of stabilizers
used in any applications where high temperatures are encountered.
High temperatures are used in the processing of tnermoplastics and
in the curing of thermoset resins and coatings. High temperatures
are also often present in the end-use applications for the
stabilized material. Low volatility will prevent loss of the
stabilizer during processing, curing, and high temperature
end-uses. Besides reducing losses of stabilizer during processing
or curing, low volatility will minimize processing problems such as
die lip build-up and plate-out.
[0012] Many polymer additives (such as ultraviolet light
stabilizers) migrate out of the polymer substrate to be protected,
or are adsorbed (chemically or physically) by one or more systems
components (such as pigments), thereby diminishing their
effectiveness. Such migration and adsorption problems are examples
of the general problems of lack of solubility and compatibility
found for many commercial polymer additives.
[0013] Bondable triazines are well known in the art. For example,
U.S. Pat. Nos. 3,423,360, 4,962,142 and 5,189,084 disclose various
bondable and the incorporation of these compounds into polymers by
chemical bonding. Bondable stabilizers have a potential advantage
in this respect in that, depending on the bondable functionality
and the particular polymer system to be stabilized, they can be
chemically incorporated into a polymer structure via reaction of
the bondable functionality either during polymer formation (such as
in the case of polymerizing monomers or a crosslinking polymer
system) or subsequently with a preformed polymer having appropriate
reactive functionality. Accordingly, due to such bonding, migration
of these UV absorbers between layers of multi-layer coatings and
into polymer substrates is greatly reduced.
SUMMARY OF THE INVENTION
[0014] The present invention provides a new class of
benzocycle-substituted pyrimidines and triazines depicted below, in
which a substituent attached to the triazine or pyrimidine ring is
a fused benzocyclic group: 1
[0015] wherein X signifies hydrogen or a blocking group, A can be a
nitrogen or optionally substituted methine, and the fused ring
designated by S is a non-aromatic 4 to 12 membered ring, optionally
containing one or more heteroatoms; any of the three rings may bear
one or more additional substituents. These fused
benzocyclic-substituted triazines and pyrimidines have the
advantage of being highly soluble in and compatible; of having
extremely low volatility, and therefore low losses during high
temperature processing or curing; of being highly effective in
inhibiting yellowing; and of being highly effective in preventing
degradation of polymers and coatings due to the action of actinic
radiation, heat, oxygen, and moisture.
[0016] The benzocyclic substituted triazine and pyrimidine UV
absorbers of the present invention possess exceptionally low
volatility, lower than most current art UV absorbers. Furthermore
these benzocyclic triazine UV absorbers, impart improved
weatherability and yellowing resistance to polymers compared to
current art UV absorbers. None of the previously available triazine
UV stabilizers and absorbers combine the unexpected low volatility
along with the weatherability, yellowing resistance, solubility,
and compatibility of the benzocyclic substituted triazine and
pyrimidine absorbers and stabilizers of the present invention.
[0017] More specifically, the new benzocycle-substituted
pyrimidines and triazines of the present invention have general
formula (I): 2
[0018] wherein
[0019] each A is independently nitrogen or methine optionally
substituted with R.sup.2, and at least two A are nitrogen;
[0020] each of T and T' is independently a direct bond, carbon,
oxygen, nitrogen, sulfur, phosphorous, boron, silicon, or
functional groups containing these elements.
[0021] X is independently selected from hydrogen and a blocking
group;
[0022] each of R.sup.1 and R.sup.2 is independently a hydrocarbyl
group, a functional hydrocarbyl group, hydroxy, alkoxy, hydrogen,
halogen, cyano, or isocyano;
[0023] each of Y, Z, R.sup.3 and R.sup.4 are independently a
hydrogen, hydrocarbyl group, a functional hydrocarbyl group,
halogen, hydroxyl, cyano, --O(hydrocarbyl), --O(functional
hydrocarbyl), --N(hydrocarbyl)(hydrocarbyl), --N(functional
hydrocarbyl)(functional hydrocarbyl), --N(hydrocarbyl)(functional
hydrocarbyl), --S(hydrocarbyl), --S(functional hydrocarbyl),
--SO.sub.2(hydrocarbyl), --SO.sub.2(hydrocarbyl),
--SO.sub.3(hydrocarbyl), --SO.sub.3(functional hydrocarbyl),
--COO(hydrocarbyl), --COO(functional hydrocarbyl),
--CO(hydrocarbyl), --CO(functional hydrocarbyl, --OCO(hydrocarbyl),
--OCO(functional hydrocarbyl), --N(hydrocarbyl)(hydrocarbyl),
--CONH.sub.2, --CONH(hyrdocarbyl), --CONH(functional hyrdocarbyl),
--CON(hydrocarbyl)(hyrdocarbyl), --CON(hydrocarbyl)(functional
hyrdocarbyl), --CON(functional hydrocarbyl)(functional
hyrdocarbyl), --S(functional hydrocarbyl), --SO.sub.2(functional
hydrocarbyl), --SO.sub.3(functional hydrocarbyl), --COO(functional
hydrocarbyl), --CO(functional hydrocarbyl), --OCO(functional
hydrocarbyl), or a hydrocarbyl group substituted by any of the
above groups;
[0024] each G is independently a direct bond, nitrogen, sulfur,
oxygen, phosphorous, boron, silicon, selenium, tellurium, or
functional groups containing these elements;
[0025] each of m, n, and o is independently an integer between 0
and 4, provided that when both G are direct bonds, the sum of m, n
and o is between 2 and 10, and that when one G is a direct bond,
the sum of m, n and o is between 1 and 9, and when neither G is a
direct bond, the sum of m, n and o is between 0 and 8;
[0026] p is an integer between 0 and 3; and
[0027] q is an integer between 0 and 20.
[0028] Preferably, T' is an oxygen atom and Y is a group L, to give
a mono-resorcinol derived benzocycle-substituted pyrimidine or
triazine of formula (II): 3
[0029] wherein
[0030] L is defined as Y, Z, R.sup.3 and R.sup.4 as defined above;
and
[0031] substituents A, G, T, X, Y, Z, R.sup.1 to R.sup.4, and
subscripts m, n, o, p, and q, are defined as above for general
formula (I).
[0032] More preferably, TZ in formula (II) is a resorcinol
derivative of formula (IIIa) or (IIIb): 4
[0033] to give a mono benzocycle bis-resorcinol derived triazine of
formulas (IVa) and (IVb): 5
[0034] More Preferably, each L in formulas III and IV are
independently selected from the group consisting of:
[0035] hydrogen;
[0036] an alkyl of 1 to 24 carbon atoms optionally substituted by
one or more hydroxy, alkoxy, carboxy, carboalkoxy, amino, amido,
carbamato, or epoxy groups, and which may contain one or more
carbonyl groups, oxygen atoms or nitrogen atoms in the chain;
[0037] an alkenyl of 2 to 24 carbon atoms optionally substituted by
one or more hydroxy, alkoxy, carboxy, carboalkoxy, amino, amido,
carbamato, or epoxy groups, and which may contain one or more
carbonyl groups, oxygen atoms or nitrogen atoms in the chain;
[0038] an aralkyl of 7 to 24 carbon atoms optionally substituted by
one or more hydroxy, alkoxy, chloro, cyano, carboxy, carboalkoxy,
amino, amido, carbamato, or epoxy groups, and which may contain one
or more carbonyl groups, oxygen atoms or nitrogen atoms in the
chain;
[0039] a polyoxyalkylene radical of the formula XII
--CH.sub.2--CH(OH)--CH.sub.2--O--(CH.sub.2--(CH.sub.2).sub.u--O--).sub.mm--
-D.sub.1 (XII)
[0040] wherein D.sub.1 is hydrogen,
[0041] --CH.sub.2--CH(OH)--CH.sub.2--OH, 6
[0042] or R.sup.25;
[0043] a polyoxyalkylene radical of the formula XIII
--CO--(CH.sub.2).sub.u--O--(CH.sub.2--(CH.sub.2).sub.u--O--).sub.mm--D.sub-
.2 (XIII)
[0044] wherein D.sub.2 is --(CH.sub.2).sub.u--CO--R.sup.22 or
R.sup.25;
[0045] a polyoxyalkylene radical of the formula VIII
--YY--O--CO--(CH.sub.2).sub.u--O--(CH.sub.2--(CH.sub.2).sub.u--O--).sub.mm-
--D.sub.3 (XIV)
[0046] wherein D.sub.3 is --(CH.sub.2).sub.u--CO--R.sup.22 or
R.sup.25;
[0047] a polyoxyalkylene radical of the formula XV
--(CH.sub.2).sub.kk--CH(R.sup.21)--CO--B.sub.1--(C.sub.nnH.sub.2nn--O--).s-
ub.mm--C.sub.nnH.sub.2nn--B.sub.1--D.sub.4 (XV)
[0048] wherein D.sub.4 is hydrogen of R.sup.25;
[0049] a polyoxyalkylene radical of the formula XVI
--CO--CH.sub.2--CH.sub.2--NH--(C.sub.nnH.sub.2nn--O--).sub.mm
--C.sub.nnH.sub.2nn--D.sub.5 (XVI)
[0050] wherein D.sub.5 is --NH.sub.2,
--NH--(CH.sub.2).sub.2--COO--R.sup.- 23 or --O--R.sup.25;
[0051] a polyoxyalkylene radical of the formula XVII
--YY--O--CO--CH.sub.2--CH.sub.2--NH--(C.sub.nnH.sub.2nn--O--).sub.mm--C.su-
b.nnH.sub.2nn--D.sub.5 (XVII)
[0052] wherein D.sub.5 is as defined under formula (XVI);
[0053] a polyoxyalkylene radical of the formula XVIII
--(C.sub.nnH.sub.2nn--O--).sub.mm--C.sub.nnH.sub.2nn--D.sub.6
(XVIII)
[0054] wherein D.sub.6 is --NH--CO--R.sup.24, --OR.sup.25, OH or
H;
[0055] a polyoxyalkylene radical of the formula XIX 7
[0056] wherein D.sub.7 is --OR.sup.25, --NHCOR.sup.24 or
--OCH.sub.2CH.sub.2OR.sup.25;
[0057] R.sup.21 is hydrogen or C.sub.1-C.sub.16 alkyl;
[0058] R.sup.22 is halogen or --O--R.sup.23;
[0059] R.sup.23 is hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.6
alkenyl, aryl, or aryl-C.sub.1-C.sub.4-alkyl;
[0060] R.sup.24 is hydrogen, C.sub.1-C.sub.12 alkyl or aryl;
[0061] R.sup.25 is C.sub.1-C.sub.16 alkyl, C.sub.5-C.sub.12
cycloalkyl, C.sub.3-C.sub.6 alkenyl, C.sub.1-C.sub.12 alkylaryl or
aryl-C.sub.1-C.sub.4 alkyl;
[0062] R.sup.26 is hydrogen or C.sub.1-C.sub.4 alkyl;
[0063] R.sup.27 is hydrogen, C.sub.1-C.sub.18 alkyl,
C.sub.3-C.sub.6 alkenyl, C.sub.1-C.sub.18 alkoxy, halogen or
aryl-C.sub.1-C.sub.4-alkyl;
[0064] R.sup.28 and R.sup.29 independently of one another are
hydrogen, C.sub.1-C.sub.18 alkyl, C.sub.3-C.sub.6 alkenyl,
C.sub.1-C.sub.18 alkoxy, or halogen;
[0065] R.sup.30 is hydrogen, C.sub.1-C.sub.4 alkyl or CN;
[0066] YY is unsubstituted or substituted C.sub.2-C.sub.20
alkyl;
[0067] kk is zero or an integer from 1-16;
[0068] B.sub.1 is O or NH;
[0069] mm is an integer from 2 to 60;
[0070] nn is an integer from 2 to 6;
[0071] u is an integer from 1 to 4.
[0072] Preferred in the present invention are compounds of formula
(IV) wherein both G are direct bonds, m=4, n, o, p and q are 0, and
all A are nitrogen of formula (IVc): 8
[0073] Even more preferred in the present invention are
bis-benzocycle-substituted pyrimidines and triazines of formula
(V): 9
[0074] wherein all substituents are as defined above for general
formulas (I) to (IV).
[0075] Most preferred in the present invention are compounds of
formula 5 wherein all G are direct bonds; m=4; n, o, p, and q are
0; and all A are nitrogen, said compound having formula: 10
[0076] wherein
[0077] L is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms,
or a functional hydrocarbyl group of 1 to 24 carbon atoms;
[0078] X is independently selected from hydrogen and a blocking
group; and
[0079] R.sup.3 and R.sup.4 are independently hydrogen, hydrocarbyl,
functional hydrocarbyl, halogen, hydroxyl, --O(hydrocarbyl),
--O(functional hydrocarbyl), --S(hydrocarbyl),
--SO.sub.2(hydrocarbyl), --SO.sub.3(hydrocarbyl),
--COO(hydrocarbyl), --CO(hydrocarbyl), --OCO(hydrocarbyl),
--N(hydrocarbyl)(hydrocarbyl), --S(functional hydrocarbyl),
--SO.sub.2(functional hydrocarbyl), --SO.sub.3(functional
hydrocarbyl), --COO(functional hydrocarbyl), --CO(functional
hydrocarbyl), ---OCO(functional hydrocarbyl), --N(functional
hydrocarbyl)(functional hydrocarbyl) or cyano.
[0080] The benzocycle-substituted pyrimidines and triazines of the
present invention further comprise oligomeric species of formulas
(VI) and (VII): 11
[0081] wherein
[0082] A, T, T', Y, Z, R.sup.1--R.sup.4, G, m-q, and X, are as
defined above;
[0083] r is an integer between 2 and 4;
[0084] D when r is 2, is selected from the group consisting of
C.sub.2-C.sub.16 alkyl, C.sub.4-C.sub.12 alkenyl, xylylene,
C.sub.3-C.sub.20 alkyl which is interrupted by one or more oxygen
atoms, hydroxy-substituted C.sub.3-C.sub.20 alkyl which is
interrupted by one or more oxygen atoms,
--CH.sub.2CH(OH)CH.sub.2O--R.sup.15--OCH.sub.2CH(OH)CH- .sub.2,
--CO--R.sup.16--CO, --CO--NH--R.sup.17--NH--CO--,
--(CH.sub.2).sub.s--COO--R.sup.18--OCO--(CH.sub.2).sub.s--
[0085] a polyoxyalkylene bridge member of the formula XX
--CH.sub.2--CH(OH)--CH.sub.2--O--(CH.sub.2--(CH.sub.2).sub.u--O--).sub.mm--
-CH.sub.2--CH(OH)--CH.sub.2-- (XX)
[0086] a polyoxyalkylene bridge member of the formula XXI
--CO--(CH.sub.2).sub.u--O--(CH.sub.2--(CH.sub.2).sub.u--O--).sub.mm--(CH.s-
ub.2).sub.u--CO-- (XXI)
[0087] a polyoxyalkylene bridge member of the formula XXII
--YY--O--CO(CH.sub.2).sub.u--O--(CH.sub.2--(CH.sub.2).sub.u--O').sub.mm--(-
CH.sub.2).sub.u--COO--YY-- (XXII)
[0088] a polyoxyalkylene bridge member of the formula XXIII
--(CH.sub.2).sub.kk--CH(R.sup.21)--CO--B.sub.1.backslash.--(C.sub.nnH.sub.-
2nn--O--).sub.mmC.sub.nnH.sub.2nn--B.sub.1--CO--CH(R.sup.21)--(CH.sub.2).s-
ub.kk-- (XXII)
[0089] a polyoxyalkylene bridge member of the formula XXIV 12
[0090] a polyoxyalkylene bridge member of the formula XXV
--YY--O--CO--(CH.sub.2).sub.2--NH--(C.sub.nnH.sub.2nn--O--).sub.mm--C.sub.-
nnH.sub.2nn--NH--(CH.sub.2).sub.2COO--YY-- (XXV)
[0091] a polyoxyalkylene bridge member of the formula XXVI
--(C.sub.nnH.sub.2nn--O--).sub.mm--C.sub.nnH.sub.2nn-- (XXVI),
[0092] and a polyoxyalkylene bridge member of the formula XXVII
--CH(CH.sub.3)--CH.sub.2--(O--CH(CH.sub.3)--CH.sub.2).sub.a--(O--CH.sub.2--
-CH.sub.2).sub.b--(O--CH.sub.2--CH(CH.sub.3).sub.c-- (XXVII)
[0093] wherein a+c=2.5 and b=8.5 to 40.5 or a+c=2 to 33 and
b=0,
[0094] R.sup.21 is hydrogen or C.sub.1-C.sub.16 alkyl,
[0095] R.sup.22 is halogen or --O--R.sup.23,
[0096] R.sup.23 is hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.3-C.sub.6
alkenyl, aryl, or aryl-C.sub.1-C.sub.4-alkyl,
[0097] R.sup.24 is hydrogen, C.sub.1-C.sub.12 alkyl or aryl,
[0098] R.sup.25 is C.sub.1-C.sub.16 alkyl, C.sub.5-C.sub.12
cycloalkyl, C.sub.3-C.sub.6 alkenyl, C.sub.1-C.sub.12 alkylaryl or
aryl-C.sub.1-C.sub.4 alkyl,
[0099] R.sup.26 is hydrogen or C.sub.1-C.sub.4 alkyl,
[0100] R.sup.27 is hydrogen, C.sub.1-C.sub.18 alkyl,
C.sub.3-C.sub.6 alkenyl, C.sub.1-C.sub.18 alkoxy, halogen or
aryl-C.sub.1-C.sub.4 alkyl,
[0101] R.sup.28 and R.sup.29 independently of one another are
hydrogen, C.sub.1-C.sub.18 alkyl, C.sub.3-C.sub.6 alkenyl, or
[0102] C.sub.1-C.sub.18 alkoxy, or halogen;
[0103] R.sup.30 is hydrogen, C.sub.1-C.sub.4 alkyl or CN,
[0104] YY is unsubstituted or substituted C.sub.2-C.sub.20
alkyl,
[0105] kk is zero or an integer from 1- 16,
[0106] B.sub.1 is O or NH,
[0107] mm is an integer from 2 to 60,
[0108] nn is an integer from 2 to 6,
[0109] u is an integer from 1 to 4;
[0110] when r is 3, D is
(CH.sub.2).sub.s--COO.sub.3R.sup.19
[0111] and when r is 4, D is
(CH.sub.2).sub.s--COO.sub.4R.sup.20
[0112] wherein R.sup.19 is C.sub.3-C.sub.10 alkanetriyl and
R.sup.20 is C.sub.4-C.sub.10 alkanetetryl; and
[0113] s is 1-6;
[0114] R.sup.15 is C.sub.2-C.sub.10 alkyl, C.sub.2-C.sub.10
oxaalkyl or C.sub.2-C.sub.10 dithiaalkyl, phenyl, naphthyl,
diphenyl, or C.sub.2-C.sub.6 alkenyl, or phenylene-XX-phenylene
wherein XX is --O--, --S--, --SO.sub.2--, --CH.sub.2--, or
--C(CH.sub.3).sub.2--;
[0115] R.sup.16 is C.sub.2-C.sub.10 alkyl, C.sub.2-C.sub.10
oxaalkyl or C.sub.2-C.sub.10 dithiaalkyl, phenyl, naphthyl,
diphenyl, or C.sub.2-C.sub.6 alkenyl provided that when r is 3 the
alkenyl has at least 3 carbons;
[0116] R.sup.17 is C.sub.2-C.sub.10 alkyl, phenyl, naphthyl,
diphenyl, or C.sub.2-C.sub.6 alkenyl, methylenediphenylene, or
C.sub.4-C.sub.15 alkylphenyl; and
[0117] R.sup.18 is C.sub.2-C.sub.10 alkyl, or C.sub.4-C.sub.20
alkyl interrupted by one or more oxygen atoms;
[0118] and 13
[0119] wherein A, T, T', Y, Z, R.sup.1--R.sup.4, G, m-q, and X, are
as defined above; r is 2 or 3; X', when r is 2, is
--CO--R.sup.16--CO--, --CO.sub.2--R.sup.16--CO.sub.2--,
--SO.sub.2--R.sup.16--SO.sub.2--, --CO--NH--R.sup.17--NH--CO--, a
polyoxyalkylene bridge member of formula
--CO--(CH.sub.2).sub.u--O--(CH.sub.2--(CH.sub.2).sub.u--O--).sub.mm--(CH.-
sub.2).sub.u--CO--, or 14
[0120] when r=3, X' is:
[0121] --(--CO.sub.2--R.sup.16)R.sup.19,
--(--CONH--R.sup.16)R.sup.19, --(--SO.sub.2--R.sup.16)R.sup.19
[0122] wherein R.sup.16, R.sup.17, R.sup.18, and R.sup.19 are as
defined above.
[0123] The benzocycle-substituted pyrimidines and triazines of the
present invention also comprise oligomeric species of the formulas
(VIII) and (IX): 15
[0124] wherein A, T, T', Y, Z, R.sup.1 through R.sup.3, G, m
through q, and X, are as defined above;
[0125] R.sup.4 is selected from the group consisting of straight
chain alkyl of 1 to 12 carbon atoms, branched chain alkyl of 1 to
12 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkyl
substituted by cyclohexyl, alkyl interrupted by cyclohexyl, alkyl
substituted by phenylene, alkyl interrupted by phenylene,
benzylidene, --S--, --S--S--, --S--E--S--, --SO--, --SO.sub.2--,
--SO--E--SO--, --SO.sub.2--E--SO.sub.2- --,
--CH.sub.2--NH--E--NH--CH.sub.2--, and 16
[0126] wherein E is selected from the group consisting of alkyl of
2 to 12 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkyl
interrupted by cyclohexyl of 8 to 12 carbon atoms, alkyl terminated
by cyclohexyl of 8 to 12 carbon atoms; and
[0127] r is an integer between 2 and 4. 17
[0128] wherein
[0129] each A is independently nitrogen or methine optionally
substituted with R.sup.2, and at least two A are nitrogen;
[0130] each of T and T' is independently a direct bond, carbon,
oxygen, nitrogen, sulfur, phosphorous, boron, silicon, or a
functional group containing these elements;
[0131] each of Y, Z, R.sup.1, and R.sup.2 is independently a
hydrocarbyl group, a functional hydrocarbyl group, hydrogen,
halogen, cyano, or isocyano;
[0132] each G is independently a direct bond, nitrogen, sulfur,
oxygen, phosphorous, boron, silicon, selenium, tellurium, or
functional groups containing these elements;
[0133] each of m, n, and o is independently an integer between 0
and 4, provided that when both G are direct bonds, the sum of m, n
and o is between 2 and 10, and that when one G is a direct bond,
the sum of m, n and o is between 1 and 9, and when neither G is a
direct bond, the sum of m, n and o is between 0 and 8;
[0134] p is an integer between 0 and 3;
[0135] q is an integer between 0 and 12;
[0136] X is independently hydrogen or a blocking group;
[0137] R.sup.3 and R.sup.4 are independently hydrogen, hydrocarbyl,
functional hydrocarbyl, halogen, hydroxyl, --O(hydrocarbyl),
--O(functional hydrocarbyl), --S(hydrocarbyl),
--SO.sub.2(hydrocarbyl), --SO.sub.3(hydrocarbyl),
--COO(hydrocarbyl), --CO(hydrocarbyl), --OCO(hydrocarbyl),
--N(hydrocarbyl)(hydrocarbyl), --S(functional hydrocarbyl),
--SO.sub.2(functional hydrocarbyl), --SO.sub.3(functional
hydrocarbyl), --COO(functional hydrocarbyl), --CO(functional
hydrocarbyl), --OCO(functional hydrocarbyl), --N(functional
hydrocarbyl)(functional hydrocarbyl) or cyano;
[0138] r is an integer between 2 and 4;
[0139] D, when r is 2, is selected from the group consisting of
C.sub.2-C.sub.16alkylene, C.sub.4-C.sub.12alkenylene, xylylene,
C.sub.3-C.sub.20alkylene which is interrupted by one or more oxygen
atoms, hydroxy-substituted C.sub.3-C.sub.20alkylene which is
interrupted by one or more oxygen atoms, --OOCR14COO--,
--CH.sub.2CH(OH)CH.sub.2O--R.- sup.15--OCH.sub.2CH(OH)CH.sub.2,
--CO--R.sup.16--CO--, --CO--NH--R.sup.17--NH--CO--, and
--(CH.sub.2).sub.s--COO--R.sup.18--OCO-- -(CH.sub.2).sub.s--;
and
[0140] when r is 3, D is
(CH.sub.2).sub.s--COO.sub.3R.sup.19
[0141] and when r is 4, D is
(CH.sub.2).sub.s--COO.sub.4R.sup.20
[0142] wherein
[0143] R.sup.19 is C.sub.3-C.sub.10alkanetriyl and R.sup.20 is
C.sub.4-C.sub.10alkanetetryl;
[0144] s is 1-6;
[0145] r is an integer between 2 and 4;
[0146] D, when r is 2, is selected from the group consisting of
C.sub.2-C.sub.16alkylene, C.sub.4-C.sub.12alkenylene, xylylene,
C.sub.3-C.sub.20alkylene which is interrupted by one or more oxygen
atoms, hydroxy-substituted C.sub.3-C.sub.20alkylene which is
interrupted by one or more oxygen atoms,
--CH.sub.2CH(OH)CH.sub.2O--R.sup.15--OCH.sub- .2CH(OH)CH.sub.2,
--CO--R.sup.16--CO--, --CO--NH--R.sup.17--NH--CO--, and
--(CH.sub.2).sub.s--COO--R.sup.18--OCO--(CH.sub.2).sub.s--; and
[0147] when r is 3, D is
(CH.sub.2).sub.s--COO.sub.3R.sup.19
[0148] and when r is 4, D is
(CH.sub.2).sub.s--COO.sub.4R.sup.20
[0149] wherein R.sup.19 is C.sub.3-C.sub.10alkanetriyl and R.sup.20
is C.sub.4-C.sub.10alkanetetryl;
[0150] s is 1-6;
[0151] R.sup.8 is C.sub.1-C.sub.18 alkyl, C.sub.3-C.sub.18 alkenyl,
C.sub.3-C.sub.20 alkyl, which is interrupted by O, N, or S, and/or
substituted by OH, C.sub.1-C.sub.4 alkyl which is substituted by
--P(O)(OR.sup.14).sub.2, --N(R.sup.9) (R.sup.10), or --OCOR.sup.11,
and/or OH, or is glycidyl, cyclohexyl or C.sub.7-C.sub.11
phenylalkyl;
[0152] R.sup.9 and R.sup.10 are each independently of the other,
C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 alkoxyalkyl,
C.sub.4-C.sub.16 dialkylaminoalkyl or C.sub.5-C.sub.12 cycloalkyl,
or R.sup.9 and R.sup.10, when taken together, are C.sub.3-C.sub.9
alkylene or C.sub.3-C.sub.9 oxaalkylene of C.sub.3-C.sub.9
azaalkylene;
[0153] R.sup.11 is C.sub.1-C.sub.18, alkyl, C.sub.2-C.sub.18
alkenyl or phenyl;
[0154] R.sup.12 is C.sub.1-C.sub.18 alkyl, C.sub.2-C.sub.18
alkenyl, phenyl, C.sub.1-C.sub.12 alkoxy, phenoxy, C.sub.1-C.sub.12
alkylamino; phenylamino, tolylamino or naphthylamino;
[0155] R.sup.13 is C.sub.1-C.sub.12 alkyl, phenyl, naphthyl or
C.sub.7-C.sub.14 alkylphenyl;
[0156] R.sup.14 is C.sub.1-C.sub.12 alkyl or phenyl;
[0157] R.sup.15 is C.sub.2-C.sub.10 alkylene phenylene or a
phenylene-x-phenylene- group, wherein X is --O--, --S--,
--SO.sub.2--, --CH--, or --C(CH.sub.3).sub.2--;
[0158] R.sup.16 is C.sub.2-C.sub.10 alkylene, C.sub.2-C.sub.10
oxaalkylene or C.sub.2-C.sub.10 dithiaalkylene, phenylene,
naphthylene, diphenylene or C.sub.2-C.sub.6 alkenylene;
[0159] R.sup.17 is C.sub.2-C.sub.10 alkylene, phenylene,
naphthylene, methylenediphenylene or C.sub.7-C.sub.15
alkylphenylene, and
[0160] R.sup.18 is C.sub.2-C.sub.10 alkylene or C.sub.4-C.sub.20
alkylene which is interrupted by one or more oxygen atoms.
[0161] The benzocycle-substituted pyrimidines and triazines of the
present invention may optionally have the added benefit of being
capable of being chemically bonded to appropriate polymer systems
via functionality attached to the benzocycle, pyrimidine and
triazine groups (e.g., by a hydroxyl, ethylenic unsaturated and/or
activated unsaturated group in one or more of R.sup.1, R.sup.2, Y
or Z).
[0162] These benzocycle-substituted pyrimidines and triazines may
in general be prepared via a number of procedures well known in the
art, for example, those described in Brunetti, H; Luethi, C.; Helv.
Chemica Acta, 55 (1972) pp. 1566-1595; Tanimoto, S.; Yamagata, M.
Senryo to Yakahin, 40 (1995) pp 339ff; U.S. Pat. Nos. 5,106,972,
5,288,868, 5,438,138, and 5,478,935; EP 395,938; EP 577,559; EP
649,841; EP 779,280; WO 9,628,431; GB 884,802; and Japanese Patent
Kokai Tokkyo Koho 9,059,263 all of which are incorporated herein by
reference for all purposes as if fully set forth.
[0163] The novel benzocycle-substituted pyrimidines and triazines
of the present invention are particularly useful as ultraviolet
light absorber agents for stabilizing a wide variety of materials
including, for example, organic compounds, oils, fats, waxes,
cosmetics, dyes and biocides, and particularly various organic
polymers (both crosslinked and non-crosslinked) used in
applications such as photographic materials, plastics, fibers or
dyed fibers, rubbers, paints and other coatings, and adhesives. The
present invention, consequently, also relates to (1) a method of
stabilizing a material which is subject to degradation by actinic
radiation (e.g., an organic material such as an organic polymer in
the form of a film, fiber, shaped article or coating) by
incorporating into said material an amount of an actinic radiation
stabilizer composition effective to stabilize the material against
the effects of actinic radiation, wherein the actinic radiation
stabilizer composition comprises the inventive
benzocycle-substituted 1,3,5-triazine or pyrimidine; and (2) the
material so stabilized.
[0164] The novel benzocycle-substituted pyrimidines and triazines
of the present invention are also effective as ultraviolet light
screening agents in applications such as sunscreens and other
cosmetic preparations, capstock layers for extruded polymers, dyed
fibers and laminated UV-screening window films, among others. The
present invention, consequently, also relates (1) to a method of
protecting a substrate against degradation by actinic radiation by
applying to the substrate an actinic radiation screening layer
(e.g., a coating film or capstock layer) containing an actinic
radiation screening composition in an amount effective to reduce
the amount of actinic radiation impinging on the substrate, wherein
the actinic radiation screening composition comprises the inventive
benzocycle-substituted pyrimidines and triazines; and (2) the
substrate so protected.
[0165] The novel benzocycle-substituted pyrimidines and triazines
of the present invention may also be employed to form light
stabilizing compositions. Such light stabilizing compositions may
include a variety of other components known in the art including
other ultraviolet light absorbers of the triazine class, other
ultraviolet light absorbers of different classes (e.g.
benzotriazoles, benzophenones), hindered amine light stabilizers,
radical scavengers, antioxidants and the like.
[0166] These and other features and advantages of the present
invention will be more readily understood by those of ordinary
skill in the art from a reading of the following detailed
description.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The Benzocycle-substituted Pyrimidines and Triazines
[0167] As used herein, the term "benzocycle-substituted pyrimidines
and triazines" broadly refers to any compound of formulas (I)
through (IX), above.
[0168] As used herein, the term "benzocycle" broadly refers to any
compound or substituent of general formula (X): 18
[0169] Wherein substituents G, R.sup.1, R.sup.2, and subscripts m,
n, o, p, and q, are defined as above for general formulas (I),
(II), (III), and (IV);
[0170] The term "hydrocarbyl" in the context of the present
invention, and in the above formulas, broadly refers to a
monovalent hydrocarbon group in which the valency is derived by
abstraction of a hydrogen from a carbon atom. Hydrocarbyl includes,
for example, aliphatics (straight and branched chain),
cycloaliphatics, aromatics and mixed character groups (e.g.,
aralkyl and alkaryl). Hydrocarbyl also includes such groups with
internal unsaturation and activated unsaturation. More
specifically, hydrocarbyl includes (but is not limited to) such
groups as alkyl, cycloalkyl, aryl, aralkyl, alkaryl, alkenyl,
cycloalkenyl and alkynyl, preferably having up to 24 carbon atoms.
A hydrocarbyl may optionally contain a carbonyl group or groups
(which is/are included in the carbon count) and/or a heteroatom or
heteroatoms (such as at least one oxygen, sulfur, nitrogen or
silicon), in the chain or ring.
[0171] The term "functional hydrocarbyl" in the context of the
present invention, and in the above formulas, broadly refers to a
hydrocarbyl possessing pendant and/or terminal reactive and/or
latent reactive functionality and/or leaving groups. "Reactive"
functionality refers to functionality which is reactive with common
monomer/polymer functionality under normal conditions well
understood by those persons of ordinary skill in the relevant art.
As non-limiting examples of reactive functionality may be mentioned
active hydrogen-containing groups such as hydroxyl, amino,
carboxyl, thio, amido, carbamoyl and activated methylene;
isocyanato; cyano; epoxy; ethylenically unsaturated groups such as
allyl and methallyl; and activated unsaturated groups such acryloyl
and methacryloyl, and maleate and maleimido (including the
Diels-Alder adducts thereof with dienes such as butadiene). "Latent
reactive" functionality within the meaning of the present invention
and, as would clearly be understood by those persons of ordinary
skill in the art, refers to reactive functionality which is blocked
or masked to prevent premature reaction. As examples of latent
reactive functionality may be mentioned ketimines and aldimines
(amines blocked, respectively, with ketones and aldehydes);
amine-carboxylate salts; and blocked isocyanates such as alcohol
(carbamates), oxime and caprolactam blocked variations. A "leaving"
group within the meaning of the present invention, as would clearly
be understood by those persons of ordinary skill in the relevant
art, is a substituent attached to the hydrocarbyl chain or ring
which during reaction is dislodged or displaced to create a valency
on a carbon or heteroatom in the hydrocarbyl chain or ring, said
valency being filled by a nucleophile. As examples of leaving
groups may be mentioned halogen atoms such as chlorine, bromine and
iodine; hydroxyl groups (protonated and unprotonated); quaternary
ammonium salts (NT.sub.4.sup.+); sulfonium salts (ST.sub.3.sup.+);
and sulfonates (--OSO.sub.3T); where T is, e.g., methyl or
para-tolyl. Of all these classes of reactive functionality, the
preferred functionality includes hydroxyl, --COOR.sup.5,
CR.sup.6.dbd.CH.sub.2, --CO--CR.sup.6.dbd.CH.sub.- 2, Cl, an
isocyanate group, a blocked isocyanate group and --NHR.sup.5,
wherein
[0172] R.sup.5 is selected from hydrogen and a hydrocarbyl
(preferably of up to 24 carbon atoms); and
[0173] R.sup.6 is selected from hydrogen and an alkyl of 1 to 4
carbon atoms (preferably hydrogen and methyl).
[0174] The term "hydrocarbylene" in the context of the present
invention is a divalent hydrocarbon group in which both valencies
derive by abstraction of hydrogens from carbon atoms. Included
within the definition of hydrocarbylene are the same groups as
indicated above for hydrocarbyl and functional hydrocarbyl with, of
course, the extra valency (for example, alkylene, alkenylene,
arylene, alkylaryl, etc.).
[0175] The term "functional hydrocarbylene" in the context of the
present invention refers to a species of hydrocarbylene possessing
pendant reactive functionality, latent reactive functionality
and/or leaving groups. The term "non-functional hydrocarbylene" in
the context of the present invention refers generally to a
hydrocarbylene other than a functional hydrocarbylene.
[0176] The benzocycle-substituted pyrimidines and triazines in
accordance with the present invention also relate to latent
stabilizing compounds against actinic radiation of the general
formulas (I), (III), and (IV), wherein at least one of the hydroxyl
groups on an aryl ring ortho to the point of attachment to the
triazine or pyrimidine ring is blocked, that is, wherein at least
one X is other than hydrogen. Such latent stabilizing compounds
liberate the effective stabilizers by cleavage of the O--X bond,
e.g., by heating or by exposure to UV radiation. Latent stabilizing
compounds are desirable because they have many favorable
properties, i.e., good substrate compatibility, good color
properties, a high cleavage rate of the O--X bond and a long shelf
life. The use of latent stabilizing compounds is further described
in U.S. Pat. Nos. 4,775,707, 5,030,731, 5,563,224 and 5,597,854,
which are incorporated herein for all purposes as if fully set
forth.
[0177] Latent stabilizing compounds comprising the
benzocycle-substituted pyrimidines and triazines in accordance with
the present invention can be prepared from compounds of the general
formulas (I), (II) and (IV) through (IX), wherein at least one X is
hydrogen, by subjecting said compounds to a further reaction to
form latent stabilizing compounds, as described in the immediately
preceding incorporated references.
[0178] As preferred examples of blocking groups X may be mentioned
one or more of the following groups: allyl, --COR.sup.a,
--SO.sub.2R.sup.b, --SiR.sup.cR.sup.dR.sup.e, --PR.sup.fR.sup.g or
--POR.sup.fR.sup.g, --CONHR.sup.h,
[0179] wherein
[0180] each R.sup.a is independently selected from C.sub.1-C.sub.8
alkyl, halogen-substituted C.sub.1-C.sub.8 alkyl, C.sub.5-C.sub.12
cycloalkyl, C.sub.2-C.sub.8 alkenyl, --CH.sub.2--CO--CH.sub.3,
C.sub.1-C.sub.12 alkoxy, and phenyl or phenoxy which is
unsubstituted or substituted by C.sub.1-C.sub.12 alkyl,
C.sub.1-C.sub.4 alkoxy, halogen and/or benzyl;
[0181] each R.sup.b is independently selected from C.sub.1-C.sub.12
alkyl, C.sub.6-C.sub.10 aryl and C.sub.7-C.sub.18 alkylaryl;
[0182] each R.sup.c, R.sup.d and R.sup.e is independently selected
from C.sub.1-C.sub.18 alkyl, cyclohexyl, phenyl and
C.sub.1-C.sub.18 alkoxy;
[0183] each R.sup.f and R.sup.g is independently selected from
C.sub.1-C.sub.12 alkoxy, C.sub.1-C.sub.12 alkyl, C.sub.5-C.sub.12
cycloalkyl, and phenyl or phenoxy which is unsubstituted or
substituted by C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.4 alkoxy,
halogen and/or benzyl; and
[0184] each R.sup.h is independently selected from C.sub.1-C.sub.8
alkyl, C.sub.5-C.sub.12 cycloalkyl, C.sub.2-C.sub.8 alkenyl,
--CH.sub.2--CO--CH.sub.3, and phenyl which is unsubstituted or
substituted by C.sub.1-C.sub.12 alkyl, C.sub.2-C.sub.8 alkenyl,
C.sub.1-C.sub.4 alkoxy, halogen and/or benzyl.
[0185] The reaction to give the latent stabilizing compounds of the
present invention of the general formula (I), (III), and (IV), in
which X is allyl, --COR.sup.a, --SO.sub.2R.sup.b,
--SiR.sup.cR.sup.dR.sup.e, --PR.sup.fR.sup.g or --POR.sup.fR.sup.g,
can be carried out, for example, by reaction of the compounds of
the general formula (III) through (X), wherein at least one X is
hydrogen with the corresponding halides such as allyl chloride,
Cl--COR.sup.a, Cl--SO.sub.2R.sup.b, Cl--SiR.sup.cR.sup.dR.sup.e,
Cl--PR.sup.fR.sup.g, or Cl--POR.sup.fR.sup.g. The reaction to give
the latent stabilizing compounds of the present invention of the
general formulas (III) through (X) in which X is --CONHR.sup.h can
be carried out, for example, by reaction of the compounds of the
general formulas (III) through (X), wherein at least one X is
hydrogen with the corresponding isocyanates. Furthermore, acylated
compounds can be obtained by reaction with anhydrides, ketenes or
esters, such as lower alkyl esters, as is well known to one skilled
in the art. The above-described reagents may be used in
approximately equimolar amounts or in excess, for example, from 2
to 20 mol with respect to the hydroxyl groups desired to be made
latent in the starting compound of the general formula (I), (III),
or (IV).
[0186] Catalysts customarily used for acylation, sulfonylation,
phosphonylation, silylation or urethanation reactions may be used
in forming the latent stabilizing benzocycle-substituted
pyrimidines and triazines of the present invention. For example,
acylation and sulfonylation reaction catalysts such as tertiary or
quaternary amines, such as triethylamine, dimethylaminopyridine or
tetrabutylammonium salts, may be used for forming these latent
stabilizing compounds.
[0187] The reaction may be carried out in the presence of a
solvent, such as relatively inert organics, e.g., hydrocarbons such
as toluene and xylene, chlorinated hydrocarbons such as carbon
tetrachloride or chloroform, or ethers such as tetrahydrofuran or
dibutyl ether, or without a solvent. Alternatively, the reagent(s)
may be employed as the solvent. The reaction temperature is usually
between room temperature and about 150.degree. C., for example, up
to the boiling point of the solvent when a solvent is used.
[0188] In preferred embodiments, each X is hydrogen.
[0189] In preferred embodiments, L is selected from the group
consisting of hydrogen, C.sub.1-C.sub.24 alkyl or mixtures thereof;
C.sub.1-C.sub.24 branched alkyl or mixtures thereof;
C.sub.3-C.sub.6 alkenyl; --COR.sup.12; --COOR.sup.12;
--CONHR.sup.12; --SO.sub.2R.sup.13; C.sub.1-C.sub.18 alkyl which is
substituted with one or more of the groups: hydroxy,
C.sub.1-C.sub.18 alkoxy, C.sub.3-C.sub.18 alkenoxy, halogen,
phenoxy, C.sub.1-C.sub.18 alkyl-substituted phenoxy,
C.sub.1-C.sub.18 alkoxy-substituted phenoxy, halogen-substituted
phenoxy, --COOH, --COOR.sup.8, --CONH.sub.2, --CONHR.sup.9,
--CON(R.sup.9)(R.sup.10), --NH.sub.2, --NHR.sup.9,
--N(R.sup.9)(R.sup.10), --NHCOR.sup.11, --N(R.sup.9)COR.sup.11,
--NHCOOR.sup.11, --N(R.sup.9)COOR.sup.11, --CN, --OCOR.sup.11,
--OC(O)NHR.sup.9, --OC(O)NHR.sup.9, --OC(O)N(R.sup.9)(R.sup.10);
C.sub.2-C.sub.50 alkyl which is interrupted by one or more oxygen
atoms or carbonyl groups and optionally substituted by one or more
substituents selected from the group consisting of hydroxy,
C.sub.1-C.sub.12 alkoxy, and glycidyloxy; glycidyl; and cyclohexyl
optionally substituted with hydroxyl or --OCOR.sup.11.
[0190] R.sup.9 and R.sup.10 independently of one another are
C.sub.1-C.sub.12 alkyl, C.sub.3-C.sub.12 alkoxyalkyl,
C.sub.4-C.sub.16 dialkylaminoalkyl, or C.sub.5-C.sub.12 cycloalkyl,
or R.sup.9 and R.sup.10 taken together are C.sub.3-C.sub.9 alkylene
or C.sub.3-C.sub.9 oxoaalkylene or C.sub.3-C.sub.9 azaalkylene.
[0191] R.sup.11 is C.sub.1-C.sub.18 alkyl, C.sub.2-C.sub.18
alkenyl, or phenyl.
[0192] Some of these groups as well as others are described in U.S.
Pat. No. 5,106,891, U.S. Pat. No. 5,189,084, U.S. Pat. No.
5,356,995, U.S. Pat. No. 5,637,706, U.S. Pat. No. 5,726,309, EP
434,608, EP 704,437, WO 96/28431, and GB 2,293,823 which are
incorporated herein by reference for all purposes as if fully set
forth.
[0193] L may also be an alkyl of 1-24 carbon atoms substituted by a
hindered amine light stabilizer (HALS) group of the general formula
XI. Triazines containing tetramethylpiperidine groups are described
in U.S. Pat. No. 4,161,592 and 5,376,710, which are hereby
incorporated by reference herein as if fully set forth. 19
[0194] wherein
[0195] J is --O--, --NR.sup.30--, --T--(CH2)2--NR.sup.30-- wherein
T is or --O-- or --S--, and R.sup.30 is C.sub.1-C.sub.12 alkyl or
hydrogen;
[0196] R.sup.31 is hydrogen or C.sub.1-C.sub.8 alkyl;
[0197] R.sup.32 is hydrogen, oxygen, C.sub.1-C.sub.21 alkoxyalkyl,
C.sub.7-C.sub.8 aralkyl, 2,3-epoxypropyl, and aliphatic acyl group
with 1-4 C atoms or one of the groups --CH.sub.2COOR.sup.33,
--CH.sub.2--CH(R.sup.34)--OR.sup.35, --COOR.sup.36 or
--CONHR.sup.36, wherein R.sup.33 is C.sub.1-C.sub.12 alkyl,
C.sub.3-C.sub.6 alkenyl, phenyl, C.sub.7-C.sub.8 aralkyl or
cyclohexyl, R.sup.34 is a hydrogen, methyl or phenyl, R.sup.35 is
hydrogen, an aliphatic, aromatic, araliphatic or alicyclic acyl
group with 1-8 C atoms, wherein the aromatic part is unsubstituted
or is substituted by chlorine, C.sub.1-C.sub.4 alkyl,
C.sub.1-C.sub.8 alkoxy or by hydroxyl, and R.sup.36 is
C.sub.1-C.sub.12 alkyl, cyclohexyl, phenyl or benzyl;
[0198] R.sup.37 is hydrogen, --OH or one of the groups
--O--CO--R.sup.38 or --NR.sup.36--CO--R.sup.38, wherein R.sup.38 is
C.sub.1-C.sub.12 alkyl or phenyl; and
[0199] K is --O--(C.sub.mmH.sub.2mm)-- wherein mm is 1 to 6,
[0200] Preferred among the sterically hindered amines are members
of the group consisting of: bis(2,2,6,6-tetramethylpiperidin-4-yl)
sebacate; bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate;
bis(1-octyloxy-2,2,6,6-- tetramethylpiperidin-4-yl)sebacate; the
condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-triazine; the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-morpholino-2,6-dichloro-1,3,5-triazine;
3-dodecyl-1-(2,2,6,6-tetramethy-
lpiperidin-4-yl)pyrrolidin-2,5-dione;
3-dodecyl-1-(1-acetyl-2,2,6,6-tetram-
ethylpiperidin-4-yl)pyrrolidin-2,5-dione; a mixture of
4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, and
mixtures thereof.
[0201] Most preferably, each L group is independently selected from
hydrogen, an alkyl of 1 to 24 carbon atoms, or mixtures thereof; an
alkyl of 4 to 20 carbon atoms containing one or more oxygen atoms
in the chain and optionally substituted with one or more hydroxyl
groups, or mixtures thereof.
[0202] Each R.sup.1 and R.sup.2 is independently selected from
hydrogen, chloro, an alkyl of 1 to 8 carbon atoms, an alkyloxy of 1
to 8 carbon atoms optionally containing an oxygen atom in the
chain, a hydroxyalkyl of 1 to 8 carbon atoms group optionally
containing an oxygen atom in the chain, a hydroxyalkyloxy of 1 to 8
carbon atoms group optionally containing an oxygen atom in the
chain, an acyl group of 2 to 12 carbon atoms and an acyloxy of 2 to
12 carbon atoms. Especially preferred is when each R.sup.1 and
R.sup.2 is independently selected from hydrogen, chloro, an alkyl
of 1 to 4 carbon atoms, and alkoxy of 1 to 4 carbon atoms, and
particularly hydrogen, methyl, and methoxy.
[0203] Each of R.sup.3 and R.sup.4 is independently selected from
hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, a
hydrocarbyloxy group of 1 to 24 carbon atoms, an acyl group of 2 to
24 carbon atoms and an acyloxy group of 2 to 24 carbon atoms. More
preferably, each R.sup.1 is independently selected from hydrogen,
an alkyl of 1 to 24 carbon atoms optionally containing an oxygen
atom in the chain; an alkyloxy of 1 to 24 carbon atoms optionally
containing an oxygen atom in the chain; an alkenyl of 2 to 24
carbon atoms optionally containing an oxygen atom in the chain; an
alkenyloxy of 2 to 24 carbon atoms optionally containing an oxygen
atom in the chain; an acyl group of 2 to 12 carbon atoms; an
acyloxy group of 2 to 12 carbon atoms; and optionally substituted
benzoyl. Still more preferably, each R.sup.1 is independently
selected from hydrogen, an alkyl of 1 to 8 carbon atoms, an
alkyloxy of 1 to 8 carbon atoms optionally containing an oxygen
atom in the chain, a hydroxyalkyl of 1 to 8 carbon atoms group
optionally containing an oxygen atom in the chain, a
hydroxyalkyloxy of 1 to 8 carbon atoms group optionally containing
an oxygen atom in the chain, an acyl group of 2 to 12 carbon atoms
and an acyloxy of 2 to 12 carbon atoms. Some of these groups as
well as others are described in U.S. Pat. No. 5,189,084, U.S. Pat.
No. 5,354,794, U.S. Pat. No. 5,543,518, U.S. Pat. No. 5,637,706, EP
434,608, EP 704,437, and WO 96/28431, which are incorporated herein
by reference for all purposes as if fully set forth.
[0204] In preferred embodiments, each of R.sup.3 and R.sup.4 is
independently selected from hydrogen, halogen, an acyl of 2 to 24
carbon atoms, benzoyl, alkyl of 1 to 24 carbon atoms, an alkenyl of
2 to 24 carbon atoms, a cycloalkyl of 5 to 24 carbon atoms; and an
aralkyl of 7 to 24 carbon atoms.
[0205] In another preferred embodiment, R.sup.3 and R.sup.4 are
independently methylene, alkylidene, or benzylidene substituted by
a benzophenone UV absorber or a benzotriazole UV absorber. Related
triazine--benzotriazole and triazine--benzophenone hybrid UV
absorbers are disclosed in U.S. Pat No. 5,585,422 which is
incorporated by reference herein for all purposes fully set forth.
In a related preferred embodiment, R.sup.3 and R.sup.4 are
independently methylene, alkylidene, or benzylidene substituted by
a second triazine UV absorber. Related triazine dimers (and
oligomers) are disclosed in U.S. Pat. No. 5,726,309 and EP 704,437
which are incorporated by reference herein for all purposes fully
set forth.
[0206] Preferred benzotriazoles comprise at least one member of the
group consisting of: 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole;
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole;
2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole;
2-(2'-hydroxy-5'-(1,1,3,- 3-tetramethylbutyl)phenyl)benzotriazole;
2-(3',5'-di-tert-butyl-2'-hydroxy- phenyl)-5-chlorobenzotriazole;
2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl-
)-5-chloro-benzotriazole;
2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)-- benzotriazole;
2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole;
2-(3',5'-di-tert-amyl-2'-hydroxphenyl)benzotriazole;
2-(3',5'-bis(.alpha.,.alpha.-dimethylbenzyl)-2'-hydroxyphenyl)-benzotriaz-
ole; a mixture of
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)-
phenyl)-5-chloro-benzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-c-
arbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-b-
enzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)pheny-
l)benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)p-
henyl)benzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl-
]-2'-hydroxyphenyl)benzotriazole,
2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl- )benzotriazole and
2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylet-
hyl)phenylbenzotriazole;
2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-b-
enzotriazol-2-ylphenol]; the transesterification product of
2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]benzotriazo-
le with polyethylene glycol 300;
[R--CH.sub.2CH--COO(CH.sub.2).sub.3].sub.- 2-- where
R.dbd.3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl; and
derivatives thereof. Most preferred benzotriazoles are members of
the group consisting of:
2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)be- nzotriazole;
2-(3',5'-di-tert-amyl-2'-hydroxphenyl)benzotriazole;
2-(3',5'-bis(.alpha.,.alpha.-dimethylbenzyl)-2'-hydroxyphenyl)-benzotriaz-
ole;
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzot-
riazole, the transesterification product of
2-[3'-tert-butyl-5'-(2-methoxy-
carbonylethyl)-2'-hydroxyphenyl]benzotriazole with polyethylene
glycol 300 and mixtures thereof.
[0207] In preferred embodiments, R.sup.11 is selected from hydrogen
and hydrocarbyl of 1 to 24 carbon atoms which may optionally be
substituted by hydroxyl or alkoxy of 1 to 4 carbon atoms and/or
contain one or more oxygen and/or nitrogen atoms in the chain. More
preferably, R.sup.11 is selected from hydrogen and hydrocarbyl of 1
to 24 carbon atoms which may optionally be substituted by hydroxyl
or alkoxy of 1 to 4 carbon atoms.
[0208] In preferred embodiments, R.sup.12 is selected from hydrogen
and an alkyl of 1 to 4 carbon atoms. More preferably, R.sup.12 is
selected from hydrogen and a methyl group.
[0209] In preferred embodiments, R.sup.13 is selected from
hydrogen, a hydrocarbyl group of 1 to 8 carbon atoms, or phenyl.
More preferably, R.sup.13 is hydrogen or methyl.
[0210] In preferred embodiments, G is a direct bond, m and o are 0,
and n is 4.
[0211] Further preferred embodiments may include any combination of
the parameters mentioned above.
Methods of Preparation
[0212] The term "Lewis acid" is intended to include aluminum
halides, alkylaluminum halides, boron halides, tin halides,
titanium halides, lead halides, zinc halides, iron halides, gallium
halides, arsenic halide, copper halides, cadmium halides, mercury
halides, antimony halides, and the like. Preferred Lewis acids
include aluminum trichloride, aluminum tribromide,
trimethylaluminum, boron trifluoride, boron trichloride, zinc
dichloride, titanium tetrachloride, tin dichloride, tin
tetrachloride, or a mixture thereof.
[0213] As used herein, the term "acid" includes any inorganic or
organic acid with at least one acidic proton, which may or may not
be dissolved in an aqueous or organic solution. The organic acids
include any organic compound that contains at least one acidic
functional group including RCO.sub.2H, RSO.sub.3H, RSO.sub.2H, RSH,
ROH, RPO.sub.3H, RPO.sub.2H, wherein R is as defined above.
Preferred protic acids include HCl, HBr, HI, HNO.sub.3, HNO.sub.2,
H.sub.2S, H.sub.2SO.sub.4, H.sub.3PO.sub.4, H.sub.2CO.sub.3, acetic
acid, formic acid, propionic acid, butanoic acid, benzoic acid,
phthalic acid, oxalic acid, malonic acid, succinic acid, glutaric
acid, adipic acid, methanesulfonic acid, and p-toluenesulfonic acid
or mixtures thereof.
[0214] As used herein, the term "step-wise" means a reaction
sequence wherein a series of reactions are conducted, the first
reaction producing compounds of Formulas (XXXII), (XXXV), or
(XXXVI) and being carried out to between about 50% to about 100%
completion prior to addition of a compound of Formula (XXXIII) to
produce compounds of Formulas (I), (IV a/b/c), or (V). Preferably
the reaction is carried out to between about 70% to about 100%
completion prior to addition of compound of Formula (XXXIII), and
more preferably to between about 75% to about 100% completion.
[0215] As used herein, the term "continuous" means a reaction
sequence not defined as "step-wise."
[0216] The novel benzocycle-substituted pyrimidines and triazines
of the present invention can be prepared through the Friedel-Crafts
reaction of a benzocycle moiety (XXX) with a halogen-substituted
pyrimidine or triazine compound of Formula (XXXI) or (XXXIV). See
Schemes 1, 2, and 3. 20
[0217] wherein Hal is bromine, chlorine, or iodine. Compound (XXX)
is defined as a protonated compound of Formula (X), as defined
above. In compounds (XXXI) and (XXXIV) Hal, is a halogen,
preferably bromine, chlorine, or iodine, and A, T, and Z are as
defined above. In compound (XXXIII) L, X, T', Y, R.sup.3, and
R.sup.4 are as defined above.
[0218] The relative amounts of the reactants are as follows. The
amount of compounds (XXXI) or (XXXIV) should be in sufficient
amounts to react with benzocyclic compounds of Formula (XXX) to
produce compounds of Formula (XXXII), (XXXV), or (XXXVI). The
amount of benzocyclic compound of Formula (XXX) is important to
ensure that a sufficient amount of benzocyclic compounds of Formula
(XXXII), (XXXV), or (XXXVI) are synthesized without excessive
amounts of undesired side products such as trisbenzocyclic triazine
or trisbenzocyclic pyrimidine. Moreover, excess amounts of
benzocyclic compounds can lead to undesired product distributions
enriched in mono- and tris-benzocyclic triazines, or mono- and
tris-benzocyclic pyrimidines thus, making product separation and
purification difficult-and resource consuming. 21
[0219] The amount of benzocyclic compounds (XXX) should be in
sufficient amounts to synthesize
2-halo-4,6-bisbenzocyclic-1,3,5-triazine, 2,4-dihalo-6-benzocyclic-
1,3,5-triazine, 2-halo-4,6-bisbenzocyclicpyrimi- dine,
2,4-dihalo-6-benzocyclicpyrimidine or convert
2-halo-4,6-bisbenzocyclic-1,3,5-triazine into
2,4,6-trisbenzocyclic-1,3,5- -triazine or convert
2-halo-4,6-bisbenzocyclicpyrimidine into
2,4,6-trisbenzocyclicpyrimidine. Preferably, there should be
between about 1 to about 5 mol equivalents of benzocyclic compound
of Formula (XXX) to compound of Formula (XXXI) or (XXXIV). The
amount of aromatic compound of Formula (XXXIII) should be between
about 0.5 to about 2.5 mol equivalents of aromatic compound of
Formula (XXXIII) to compounds of Formula (XXXII), (XXXV), or
(XXXVI).
[0220] The amount of Lewis acid, Al(Hal).sub.3 wherein Hal is a
halide as defined above, used in the reaction should be in
sufficient amounts to transform 2,4,6-trihalo-1,3,5-triazine or
2,4,6-trihalo-pyrimidine to the preferred
2-halo-4,6-bisbenzocyclic-1,3,5-triazine,
2,4,6-trisbenzocyclic-1,3,5-triazine, or
2-halo-4,6-bisbenzocyclicpyrimid- ine,
2,4,6-trisbenzocyclicpyrimidine, respectively. The amount of Lewis
acid should be between about 0.5 to about 500 mol equivalents.
Preferably, the amount of Lewis acid should be between about 1 to
about 5 mol equivalents. 22
[0221] Advantageously, an acid can be used in conjunction with a
Lewis acid when synthesizing compounds of Formula (I), (IV a/b/c),
(V), (XXXII), (XXXV), or (XXXVI). The amount of acid used in the
reaction should be in sufficient amounts to transform
2,4,6-trihalo-1,3,5-triazine or 2,4,6-trihalopyrimidine to the
preferred 2-halo-4,6-bisbenzocyclic-1,3- ,5-triazine or
2-halo-4,6-bisbenzocyclicpyrimidine, respectively, or convert
2-halo-4,6-bisbenzocyclic-1,3,5-triazine or
2-halo-4,6-bisbenzocyclicpyrimidine to the compounds of Formula
(I), (IV a/b/c), or (V), as desired. Preferably, the amount of acid
should be between about 0.01 mol to about 5 mol equivalents.
[0222] For all synthetic schemes, the Lewis acid and acid
preferably combine to form a mixture that can be prepared in situ
or pre-formed prior to addition to the reagents. The Lewis acid
and/or acid can be combined with either the benzocyclic compound of
Formula (XXX), compounds of Formula (XXXI) or (XXXIV), or both, in
any manner. In situ reaction mixture preparation comprises addition
of at least one Lewis acid and at least one acid to at least one
compound of Formula (XXXI) or (XXXIV), at least one benzocyclic
compound of Formula (XXX), and optionally solvent, without regard
to addition order. To prepare the mixture prior to addition to the
reagents, i.e., the pre-formed method, at least one Lewis acid and
at least one acid are combined and allowed to mix prior to
addition, optionally in an inert solvent. Thereafter, the mixture
is added to the reagents or vice versa, as desired and in any
addition order. As used herein, one or more Lewis acids may be
used, the first step and the second step Lewis acid may be the same
or different. Additionally, one or more acids may be used, the
first step and second step acid may be the same or different. In
the "continuous" process, the use of additional Lewis acid, acid,
or both is optional.
[0223] If the complex is prepared using the pre-formed method,
preferred mixing time of the Lewis acid and acid, prior to addition
to the reagents, is between about 1 minute to about 5 hours, more
preferred time is between about 10 minutes to about 2 hours. The
preferred mixing temperature of the Lewis acid and acid mixture,
prior to addition to the reagents, is between about -50.degree. C.
to about 100.degree. C., more preferred is between about
-10.degree. C. to about -50.degree. C.
[0224] The reaction should run for a sufficient amount of time, at
a sufficient temperature and pressure to synthesize the desired
triazine or pyrimidine compound. The preferred reaction time for
the synthesis of compounds of Formula (XXXII), (XXXV), (XXXVI),
i.e., the first step, is between about 5 minutes and about 48
hours, more preferred between about 15 minutes and about 24 hours.
The preferred reaction time for the synthesis of compounds of
Formula (I), (IV a/b/c), (V), i.e., the second step, is between
about 10 minutes and about 24 hours, more preferably time is
between about 30 minutes and about 12 hours. The preferred reaction
temperature for the first step is between about -50.degree. C. and
about 150.degree. C., more preferred reaction temperature between
about -30.degree. C. and about 50.degree. C. The reaction pressure
is not critical and can be about 1 atm or higher if desired.
Preferably, the reaction is carried out under an inert gas such as
nitrogen or argon. The preferred reaction temperature for the
second step is between about 0.degree. C. and about 120.degree. C.,
a more preferred reaction temperature is between about 20.degree.
C. and about 100.degree. C.
[0225] The step-wise process comprises mixing at least one Lewis
acid, at least one acid, and compounds of Formula (XXXI) or (XXXIV)
with one or more of the desired benzocyclic compounds of Formula
(XXX), preferably until the reaction is between about 70% to about
100% completed. Thereafter, the product is isolated and purified.
The aromatic compound of Formula (XXXIII) is added to the purified
product along with Lewis acid and optionally an acid to synthesize
the compounds of Formula (I), (IV a/b/c), or (V). The step-wise
sequence allows for the isolation, purification, and storage of
compounds of Formula (XXXII), (XXXV), or (XXXVI) prior to
subsequent reaction with aromatic compounds of Formula
(XXXIII).
[0226] The continuous reaction comprises allowing a compound of
Formula (XXXI) or (XXXIV) to react with one or more benzocyclic
compounds of Formula (XXX) in the presence of at least one Lewis
acid and at least one acid preferably until the reaction is between
about 70% to about 100% complete. Thereafter, without isolating the
product of Formula (XXXII), (XXXV), or (XXXVI), the aromatic
compound of Formula (XXXIII) is allowed to react with the product
of Formula (XXXII), (XXXV), or (XXXVI) in the presence of
optionally at least one second Lewis acid and optionally at least
one second acid preferably until the reaction is between about 70%
to about 100% complete. The continuous reaction eliminates the need
to purify the intermediate product of Formula (XXXII), (XXXV), or
(XXXVI) or use of additional reagents such as solvents, and
optionally Lewis acids and acids. Moreover, the one-step process
simplifies the synthetic reaction pathway such that no unnecessary
handling or processing of the reaction mixture is required until
the reaction is completed.
[0227] To synthesize compounds of Formula (I), (IV a/b/c) or (V)
using the pre-formed method, the preferred addition time of the
Lewis acid/acid mixture to a reagent mixture is between about 5
minutes to about 5 hours, more preferred time is between about 15
minutes to about 3 hours. The addition temperature of the Lewis
acid/acid mixture to a reagent mixture is between about -50.degree.
C. to about 150.degree. C., preferred addition temperature is
between about -30.degree. C. to about 50.degree. C., and more
preferred addition temperature is between about -20.degree. C. to
about 80.degree. C.
[0228] To synthesize compounds of Formula (I), (IV a/b/c), or (V)
using the pre-formed method, the preferred addition temperature of
the Lewis acid/acid mixture is between about 0.degree. C. to about
100.degree. C., preferred addition temperature is between about
20.degree. C. to about 80.degree. C.
[0229] To synthesize compounds of Formula (I), (IV a/b/c), (V), the
preferred addition time of the aromatic compound of Formula
(XXXIII) to the reaction mixture is between about 5 minutes to
about 10 hours, more preferred addition time is between about 10
minutes to about 5 hours, and most preferred addition time is
between about 15 minutes to about 2 hours. The addition temperature
of the aromatic compound of Formula (XXXIII) to the reaction
mixture is between about 0.degree. C. to about 150.degree. C.,
preferred addition temperature is between about 20.degree. C. to
about 100.degree. C.
[0230] The Lewis acid/acid mixture should be present in amounts
sufficient to react with the number of halogens being substituted
on compounds of Formula (XXXI) or (XXXIV). A range of between about
1 to about 5 mol equivalents of Lewis acid and a range of between
about 0.01 mol to about 5 mol equivalents of acid can be used. The
preferred Lewis acid is aluminum chloride. A preferred amount of
Lewis acid is between about 2 to about 4 mol equivalents to
halo-triazine or halo-pyrimidine. A preferred amount of acid is
between about 0.05 mol to about 2 mol equivalents to compounds of
Formula (XXXI) or (XXXIV).
[0231] The synthesis of compounds of Formula (VI), (VII), VIII), or
(IX) can be performed by methods commonly known in the art. One of
ordinary skill in the art with little or no experimentation can
determine the appropriate conditions to obtain the polymer product
desired.
Uses of the Benzocycle-substituted Pyrimidines and Triazines
[0232] As indicated earlier, the novel benzocyclie-substituted
pyrimidines and triazines of the present invention are particularly
useful as ultraviolet light absorber agents for stabilizing a wide
variety of materials including, for example, various polymers (both
crosslinked and thermoplastic), photographic materials and dye
solutions for textile materials, as well as in ultraviolet light
screening agents (such as sunscreens). The novel
benzocyclie-substituted pyrimidines and triazines of the present
invention can be incorporated into such material in any one of a
variety of conventional manners, including for example, physical
mixing or blending, optionally, with chemical bonding to the
material (typically to a polymer), as a component in a light
stabilizing composition such as a coating or solution, or as a
component in a UV screening composition such as a sunscreen
composition.
[0233] In one embodiment of the present invention, the
benzocyclie-substituted pyrimidines and triazines of the present
invention can be employed to stabilize materials which are subject
to degradation by ultraviolet radiation by incorporating the
presently claimed compounds into polymeric materials, either
chemically or physically. Non-limiting examples of polymeric
materials that may be so stabilized are polyolefins, polyesters,
polyethers, polyketones, polyamides, natural and synthetic rubbers,
polyurethanes, polystyrenes, high-impact polystyrenes,
polyacrylates, polymethacrylates, polyacetals, polyacrylonitriles,
polybutadienes, polystyrenes, ABS, SAN (styrene acrylonitrile), ASA
(acrylate styrene acrylonitrile), cellulosic acetate butyrate,
cellulosic polymers, polyimides, polyamideimides, polyetherimides,
polyphenylsulfides, PPO, polysulfones, polyethersulfones,
polyvinylchlorides, polycarbonates, polyketones, aliphatic
polyketones, thermoplastic TPO's, aminoresin crosslinked
polyacrylates and polyesters, polyisocyanate crosslinked polyesters
and polyacrylates, phenol/formaldehyde, urea/formaldehyde and
melamine/formaldehyde resins, drying and non-drying alkyd resins,
alkyd resins, polyester resins, acrylate resins cross-linked with
melamine resins, urea resins, isocyanates, isocyanurates,
carbamates, and epoxy resins, cross-linked epoxy resins derived
from aliphatic, cycloaliphatic, heterocyclic and aromatic glycidyl
compounds, which are cross-linked with anhydrides or amines,
polysiloxanes, Michael addition polymers, amines, blocked amines
with activated unsaturated and methylene compounds, ketimines with
activated unsaturated and methylene compounds, polyketimines in
combination with unsaturated acrylic polyacetoacetate resins,
polyketimines in combination with unsaturated acrylic resins,
radiation curable compositions, epoxymelamine resins, organic dyes,
cosmetic products, cellulose-based paper formulations, photographic
film paper, ink, and blends thereof.
[0234] The preferred polymeric material is selected from the group
consisting of polyolefins; copolymers of one or more monoolefins
and/or diolefins with carbon monoxide and/or with other vinyl
monomers; hydrocarbon resins (such as C.sub.5-C.sub.9) including
hydrogenated modifications thereof and mixtures of polyalkylenes
and starch; polyesters; copolyethers esters; polyethers;
polyketones; polyamides and copolyamides derived from diamines,
dicarboxylic acids and/or aminocarboxylic acids or the
corresponding lactams; natural and synthetic rubbers and
elastomers; polyurethanes; polystyrenes,
poly-.alpha.-methylstyrenes and copolymers with other vinyl
monomers; graft copolymers of styrene; high impact polystyrenes;
polyacrylic acids, polymethacrylics acids, polyacrylates,
polymethacrylates, polyacrylamides, polyacrylonitriles; homo- and
copolymers derived from unsaturated alcohols and amines or the acyl
derivatives or acetals thereof such as polyvinyl alcohol, polyvinyl
acetate, polyacetals, and polybutyrals; homo- and copolymers of
cyclic ethers such as alkylene glycols and alkylene oxides, as well
as copolymers with bisglycidyl ethers; polybutadienes;
polystyrenes; ABS (acrylonitrile butadiene styrene); SAN (styrene
acrylonitrile); ASA (acrylate styrene acrylonitrile); cellulosic
acetate butyrate; cellulosic polymers; polyureas; polyimides;
polyamides-imides; polyester-imides; polyether-imides;
polyhydantoins; polybenzimidazoles; polyphenylsulfide; PPO
(polypropylene oxide); polysulfones; polyether sulfones; polyether
ketones; halogen-containing polymers; polyvinylchlorides;
polycarbonates; polyester carbonates; thermoplastic TPO's; amino
resin cross-linked polyacrylates and polyesters; polyisocyante
cross-linked polyesters and polyacrylates; phenol/formaldehyde,
urea/formaldehyde and melamine/formaldehyde resins; saturated and
unsaturated polyester resins; cross-linkable acrylic resins derived
from substituted acrylates such as epoxy acrylates, hydroxy
acrylates, isocyanato acrylates, urethane acrylates or polyester
acrylates; alkyd resins, polyester resins, and acrylate resins
cross-linked with melamine resins, urea resins, isocyantes,
isocyanurates, carbamates, or epoxy resins; cross-linked epoxy
resins derived from aliphatic cycloaliphatic, heterocyclic and/or
aromatic glycidyl compounds which are cross-linked with anhydrides
or amines; polysiloxanes; Michael addition polymers of amines or
blocked amines (e.g., ketimines) with activated unsaturated and/or
methylene compounds; of ketimines with activated unsaturated and/or
methylene compounds such as acrylates and methacrylates, maleates,
and acetoacetates; polyketimines in combination with unsaturated
acrylic polyacetoacetate resins or with unsaturated acrylic resins;
radiation curable compositions; epoxymelamine resins; natural
polymers such as cellulose, rubber, gelatin, and chemically
modified derivatives thereof; organic dyes and pigments; any
mixture or blends of the above; cosmetic products; cellulose-based
paper formulations; photographic film; paper; ink; and intraocular
lenses.
[0235] Further non-limiting examples of specific polymers which may
be stabilized include:
[0236] 1. Homo- and copolymers of monoolefins and diolefins
including but not limited to ethylene, propylene, isobutylene,
butene, methylpentene, hexene, heptene, octene, isoprene,
butadiene, hexadiene, dicyclopentadiene, ethylidene and
cycloolefins such as cyclopentene and norbornene; for example,
polyethylenes (which optionally can be crosslinked) such as high
density polyethylene (HDPE), high density and high molecular weight
polyethylene (HDPE-HMW), high density and ultrahigh molecular
weight polyethylene (HDPE-UHMW), medium density polyethylene
(MDPE), low density polyethylene (LDPE), linear low density
polyethylene (LLDPE) and branched low density polyethylene
(BLDPE).
[0237] 2. Copolymers of one or more monoolefins and/or diolefins
with carbon monoxide and/or with other vinyl monomers, including
acrylic and methacrylic acid, acrylates and methacrylates,
acrylamides, acrylonitriles, styrenes, vinyl acetate (such as
ethylene/vinyl acetate copolymers), vinyl halides, vinylidene
halides, maleic anhydride and allyl monomers such as allyl alcohol,
allyl amine ally glycidyl ether and derivatives thereof.
[0238] 3. Hydrocarbon resins (such as C.sub.5-C.sub.9) including
hydrogenated modifications thereof and mixtures of polyalkylenes
and starch.
[0239] 4. Homo- and copolymers of styrenes such as styrene,
p-methylstyrene and .alpha.-methylstyrene.
[0240] 5. Copolymers of one or more styrenes with other vinyl
monomers such as olefins and diolefins (e.g., ethylene, isoprene
and/or butadiene), acrylic and methacrylic acid, acrylates and
methacrylates, acrylamides, acrylonitriles, vinyl acetate (such as
ethylene/vinyl acetate copolymers), vinyl halides, vinylidene
halides, maleic anhydride and allyl compounds such as allyl
alcohol, allyl amine allyl glycidyl ether and derivatives
thereof.
[0241] 6. Graft copolymers of styrenes on polybutadienes,
polybutadiene/styrene copolymers and polybutadiene/acrylonitrile
copolymers; styrene (or .alpha.-methylstyrene) and acrylonitrile
(or methacrylonitrile) on polybutadiene; styrene and maleic
anhydride on polybutadiene; styrene, acrylonitrile and maleic
anhydride or maleimide on polybutadiene; styrene and acrylonitrile
on ethylene/propylene/diene copolymers; styrene and acrylonitrile
on polyalkyl acrylates or methacrylates; and styrene and
acrylonitrile on acrylate/butadiene copolymers.
[0242] 7. Halogen-containing polymers such as polychloroprene;
chlorinated rubbers; chlorinated and brominated
isobutylene/isoprene copolymers; chlorinated or sulfochlorinated
polyethylene; copolymers of ethylene and chlorinated ethylene;
epichlorohydrin polymers and copolymers; and polymers and
copolymers of halogen-containing vinyl compounds such as vinyl
chloride, vinylidene chloride, vinyl fluoride and/or vinylidene
fluoride and other vinyl monomers.
[0243] 8. Homo- and copolymers derived from
.alpha.,.beta.-unsaturated acids and derivatives thereof such as
acrylic acid, methacrylic acid, acrylates, methacrylates,
acrylamides and acrylonitriles.
[0244] 9. Copolymers of the monomers mentioned in (8) with other
unsaturated monomers such as olefins and diolefins (e.g.,
butadiene), styrenes, vinyl halides, maleic anhydride and allyl
monomer such as allyl alcohol, allyl amine, allyl glycidyl ether
and derivatives thereof.
[0245] 10. Homo- and copolymers derived from unsaturated alcohols
and amines or the acyl derivatives or acetals thereof, such as
vinyl alcohol, vinyl acetate, vinyl stearate, vinyl benzoate, vinyl
maleate, vinyl butyral, allyl alcohol, allyl amine, allyl glycidyl
ether, allyl phthalate and allyl melamine; as well as copolymers of
such monomers with other ethylenically unsaturated monomers
mentioned above.
[0246] For the preceding groups 1-10 of polymers, the present
invention further encompasses these polymers as prepared by
metallocene catalysts.
[0247] 11. Homo- and copolymers of cyclic ethers such as alkylene
glycols and alkylene oxides, as well as copolymers with bisglycidyl
ethers.
[0248] 12. Polyacetals such as polyoxymethylene and those
polyoxymethylenes which contain ethylene oxide as a comonomer; and
polyoxymethylenes modified with thermoplastic polyurethanes,
acrylates and/or MBS.
[0249] 13. Polyphenylene oxides and sulfides.
[0250] 14. Polyurethanes derived from hydroxy-functional components
such as polyhydric alcohols, polyethers, polyesters, polyacrylics
and/or polybutadienes on the one hand, and aliphatic and/or
aromatic isocyanates on the other, as well as precursors
thereof.
[0251] 15. Polyamides and copolyamides derived from diamines,
dicarboxylic acids and/or aminocarboxylic acids or the
corresponding lactams, such as polyamide 4, polyamide 6, polyamide
6/6, polyamide 6/10, polyamide 6/9, polyamide 6/12, polyamide 4/6,
polyamide 12/12, polyamide 11 and polyamide 12; aromatic polyamides
starting from m-xylene diamine and adipic acid; polyamides prepared
from hexamethylene diamine and isophthalic and/or terephthalic acid
and with or without an elastomer as a modifier, for example,
poly-2,4,4-trimethylhexamethylene terephthalamide or
poly-m-phenylene isophthalamide; block copolymers of the
aforementioned polyamides with polyolefins, olefin copolymer,
ionomers, chemically bonded or grafted elastomers, or polyethers
such as polyethylene glycol, polypropylene glycol or
polytetramethylene glycol; and polyamides condensed during
processing (RIM polyamide systems).
[0252] 16. Polyureas, polyimides, polyamide-imides,
polyetherimides, polyesterimides, polyhydantoins and
polybenzimidazoles.
[0253] 17. Polyesters derived from dicarboxylic acids, diols and/or
hydroxycarboxylic acids or the corresponding lactones, such as
polyethylene terephthalate, polybutylene terephthalate,
poly-1,4-dimethylcyclohexane terephthalate and
polyhydroxybenzoates, as well as block copolyether esters derived
from hydroxyl-terminated ethers; PETG; PEN; PTT; and also
polyesters modified with polycarbonate or MBS.
[0254] 18. Polycarbonates and polyester carbonates.
[0255] 19. Polysulfones, polyether sulfones and polyether
ketones.
[0256] 20. Crosslinked polymers derived from aldehydes condensation
resins such as phenol/formaldehyde resins, urea/formaldehyde resins
and melamine/formaldehyde resins.
[0257] 21. Drying and non-drying alkyd resins.
[0258] 22. 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.
[0259] 23. Crosslinkable acrylic resins derived from substituted
acrylates such as epoxy acrylates, hydroxy acrylates, isocyanato
acrylates, urethane acrylates or polyester acrylates.
[0260] 24. Alkyd resins, polyester resins and acrylate resins
crosslinked with melamine resins, urea resins, isocyanates,
isocyanurates, carbamates or epoxy resins.
[0261] 25. Crosslinked epoxy resins derived from aliphatic,
cycloaliphatic, heterocyclic and/or aromatic glycidyl compounds
such as bisphenol A and bisphenol F, which are crosslinked with
hardeners such as anhydrides or amines.
[0262] 26. Natural polymers such as cellulose, rubber, gelatin and
chemically modified homologous derivatives thereof, including
cellulose acetates, cellulose propionates and cellulose butyrates,
or the cellulose ethers such as methyl cellulose, as well as rosins
and their derivatives.
[0263] 27. Polysiloxanes.
[0264] 28. Michael addition polymers of amines or blocked amines
(e.g., ketimines) with activated unsaturated and/or methylene
compounds such as acrylates and methacrylates, maleates and
acetoacetates.
[0265] 29. Mixtures or blends of any of the above, such as PP/EPDM,
polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS,
PC/ASA, PC/PBT, PVC/CPE, PVC/acrylate, POM/thermoplastic PUR,
PC/thermoplastic polyurethane, POM/acrylate, POM/MBS, PPO/HIPS,
PPO/PA6.6 and copolymers, PATENT/HDPE, PP/HDPE, PP/LDPE, LDPE/HDPE,
LDPE/EVA, LDPE/EAA, PATENT/PP, PATENT/PPO, PBT/PC/ABS, PBT/PET/PC
and the like.
[0266] 30. Polyketimines in combination with unsaturated acrylic
polyacetoacetate resins or with unsaturated acrylic resins
including urethane acrylates, polyether acrylates, vinyl or acryl
copolymers with pendant unsaturated groups and acrylated
melamines.
[0267] 31. Radiation curable compositions containing ethylenically
unsaturated monomers or oligomers and a polyunsaturated aliphatic
oligomer.
[0268] 32. Epoxymelamine resins such as light-stable epoxy resins
cross-linked by an epoxy functional coetherified high solids
melamine resin.
[0269] Other materials which can be stabilized include, for
example:
[0270] 33. Naturally occurring and synthetic organic materials
which may be mixtures of compounds, including mineral oils, animal
and vegetable fats, oils and waxes, or oils, fats or waxes based on
synthetic esters (e.g., phthalates, adipates, phosphates or
trimellitates) and also mixtures of synthetic esters with mineral
oils in any ratio.
[0271] 34. Aqueous emulsions of natural or synthetic rubber such as
natural latex or lattices of carboxylated styrene/butadiene
copolymers.
[0272] 35. Organic dyes such as azo dyes (diazo, triazo and
polyazo), anthraquinones, benzodifuranones, polycyclic aromatic
carbonyl dyes, indigoid dyes, polymethines, styryl dyes, di- and
triaryl carbonium dyes, phthalocyanines, quinophthalones, sulfur
dyes, nitro and nitroso dyes, stilbene dyes, formazan dyes,
quinacridones, carbazoles and perylene tetracarboxylic
diimides.
[0273] 36. Cosmetic products, such as skin lotions, collagen
creams, sunscreen, facial make-up, etc., comprising synthetic
materials such as antioxidants, preservatives, lipids, solvents,
surfactants, colorants, antiperspirants, skin conditioners,
moisturizers etc.; as well as natural products such as collagen,
proteins, mink oil, olive oil, coconut oil, carnauba wax, beeswax,
lanolin, cocoa butter, xanthan gum, aloe, etc.
[0274] 37. Cellulose-based paper formulations for use, e.g., in
newsprint, cardboard, posters, packaging, labels, stationery, book
and magazine paper, bond typing paper, multi-purpose and office
paper, computer paper, xerographic paper, laser and ink-jet printer
paper, offset paper, currency paper, etc.
[0275] 38. Photographic film paper.
[0276] 39. Ink.
ALIPHATIC POLYAMIDE
[0277] The novel benzocyclie-substituted pyrimidines and triazines
of the present invention can also be used with aliphatic polyamide
polymers. An "Aliphatic polyamide" is a polyamide characterized by
the presence of recurring carbonamide groups as an integral part of
the polymer chain which are separated from one another by at least
two aliphatic carbon atoms. Illustrative of these polyamides are
those having recurring monomeric units represented by the general
formula:
--NHC(O)RC(O)NHR.sup.1-- or --NH--R--C(O)--
[0278] or a combination hereof in which R and R.sup.1 are the same
or different and are alkylene groups of at least about two carbon
atoms, preferably alkylene having from about 2 to about 12 carbon
atoms. Exemplary of such polyamides are polyamides formed by the
reaction of diamines and diacids such as poly (tetramethylene
adipamide)(nylon 4,6); poly(hexamethylene adipamide) (nylon 6,6);
poly (hexamethylene azelamide) (nylon 6,9); poly(hexamethylene
sebacamide) (nylon 6,10); poly(heptamethylene pimelamide) (nylon
8,8); poly(nonamethylene azelamide) (nylon 9,9); poly(decamethylene
azelamide) (nylon 10,9); and the like. Also illustrative of useful
aliphatic polyamides are those formed by polymerization of amino
acids and derivatives thereof, as for example lactams. Illustrative
of these useful polyamides are poly(4-aminobutyric acid) (nylon 4);
poly(6-aminohexanoic acid) (nylon 6); poly(7-aminoheptanoic acid)
(nylon 7); poly(8-aminoocatanoic acid) (nylon 8);
poly(9aminononanoic acid) (nylon 9); poly(10-aminodecanoic acid)
(nylon 10); poly(11-aminoundecanoic acid) (nylon 11);
poly(12-aminododecanoic acid) (nylon 12); and the like. Blends of
two or more aliphatic polyamides may also be employed.
[0279] Copolymers formed from any combination of the recurring
units of the above referenced aliphatic polyamides can be used. By
way of illustration and not limitation, such aliphatic polyamide
copolymers include caprolactam/hexamethylene adipamide copolymer
(nylon 6/6,6); hexamethylene adipamide/caprolactam copolymer (nylon
6, 6/6); hexamethylene adipamide/hexamethylene-azelamide copolymer
(nylon 6,6/6,9); and copolymers formed from recurring units of the
above referenced aliphatic polyamides with aliphatic/aromatic
polyamide recurring units may also be used. Examples of such
copolyamides are nylon 6/6T; nylon 6,6/6, T; nylon 6/10T; nylon
6/12T; nylon 6,10/6,T etc.
[0280] Preferred aliphatic polyamides for use in the practice of
this invention are poly(caprolactam); poly(7-aminoheptanic acid);
poly(tetramethylene adipamide); poly(hexamethylene adipamide); and
mixtures thereof. The particularly preferred aliphatic polyamides
are poly(caprolatam); poly(hexamethylene adipamide);
poly(tetramethylene adipamide); and mixtures thereof.
[0281] Aliphatic polyamides useful in the practice of this
invention may be obtained from commercial sources or prepared in
accordance with known preparatory techniques. For example,
polycaprolactam may be obtained from Allied Signal Inc. and
poly(hexamethylene adipamide) may be obtained from DuPont Co.
[0282] The number average molecular weight of the aliphatic
polyamide may vary widely. Usually, the aliphatic polyamide is of
film forming molecular weight that is sufficiently high to form a
free standing film and sufficiently low to allow melt processing of
the blend into a film. Such number average molecular weights are
well known to those of skill in the film art and are usually at
least about 5,000 as determined by the formic acid viscosity
method. In this method, a solution of 9.2 wt. Concentration of
aliphatic polyamide in 90% formic acid at 25.degree. C. is used. In
the preferred embodiments of the invention, the number average
molecular weight of the aliphatic polyamide is from about 5,000 to
about 1,000,000 and in the particularly preferred embodiments is
from about 10,000 to about 100,000. Amongst the particularly
preferred embodiments, most preferred are those in which the
molecular weight of the aliphatic polyamide is from about 20,000 to
about 40,000.
POLYURETHANE
[0283] Polyurethane (PUR) elastomer products ("spandex") can be
stabilized against discoloration and loss of elasticity during UV
light exposure with combinations of UV absorbers according to the
invention and hindered amine light stabilizers. Spandex fibers is a
PUR elastomer product, which requires very specific UV absorber and
hindered amine light stabilizers properties in order to achieve
optimum performance. UV absorbers of the triazine class of this
invention can be combined with polymeric hindered amine light
stabilizers (HALS) to provide outstanding performance in achieving
the desired properties for the Spandex fiber applications.
[0284] The triazine UV absorber of the invention, used alone or in
combination with HALS provides the following properties in the
Spandex fiber application: (1) low color contribution at typical
use levels in the 0.5-2.0% range; (2) sufficient MW, thermal
stability and low volatility for fiber processing and thermal
exposure conditions; (3) high compatibility and permanence; (4)
prevent discoloration and loss of elasticity during exposure to UV
light energy; (5) low extraction by water and dry cleaning
solvents; (6) low color development during exposure to atmospheric
pollutants, NO.sub.x, SO.sub.x, hydrocarbons, etc.; (7) low
interaction with sea water and pool chemicals; (8) low interaction
and color development with typical phenolic antioxidants used for
the thermal stabilization of Spandex fibers; and (9) low
interaction with copper based antioxidant systems used in Nylon
fibers for Nylon/Spandex fabrics.
[0285] The triazine UV absorber with or without the polymeric HALS
provides outstanding stabilization with minimum negative effect on
secondary performance properties, such as low color development
during NO.sub.x exposure and low interaction with copper based
antioxidant systems using in Nylon fibers.
[0286] As noted above, any of the triazine compounds disclosed
herein can be used to impart one or more of the properties
described above to Spandex fibers when added thereto in a
stabilization effective amount.
[0287] Preferably, these triazine compounds are added in
combination with polymeric HALS. The polymeric HALS is preferably
poly[(6-morpholino-s-tri-
azine-2,4-diyl)[2,2,6,6,-tetramethyl-4-piperidyl)imino]-hexamethylene
[(2,2,6,6-tetramethyl-4-piperidyl)imino]]. Most preferably, the
polymeric HALS is the methylated (M) version of the above HALS,
which is sold by Cytec Industries, Inc. as CYASORB.RTM.UV-3529
light stabilizer. Other polymeric HALS disclosed in U.S. Pat. No.
4,331,586 are also suitable.
[0288] Spandex fibers are made from a polyurethane (PUR) prepolymer
prepared from a diisocyanate and a glycol. There are four basic
processes used to convert the PUR prepolymer into the fiber
product. These processes are Solution Dry Spinning, Solution Wet
Spinning, Melt Extrusion, and Reaction Spinning. The above UV
stabilizer alone or in combination with HALS would be suitable for
use in any or all four processes.
[0289] Spandex fibers may contain a processing antioxidant system,
such as a phenolic antioxidant, or a phenolic/phosphite antioxidant
combination. In addition, pigments, such as TiO.sub.2 are commonly
used in the fiber products.
[0290] The triazine UV absorber alone or with M-HALS can be
dissolved into DMF or DMAC and added to the PUR prepolymer solution
prior to solution fiber spinning processes. Also, the combination
can be extrusion compounded into the PUR compound used in the melt
spinning process.
POLYCARBONATES
[0291] Among polymeric materials to be stabilized with the novel
benzocycle-substituted pyrimidines and triazines of the present
invention, preference is given to the polycarbonates, polyesters,
polyamides, polyacetals, polyphenylene oxides and polyphenylene
sulfides, but especially to the polycarbonates. Those compounds are
to be understood as being especially those polymers the
constitutional repeating unit of which corresponds to the formula:
23
[0292] wherein A is a divalent phenolic radical. Examples of A are
given inter alia in U.S. Pat. No. 4,960,863 and
[0293] DE-A-3 922,496. A can be derived, for example, from
hydroquinone, resorcinol, dihydroxybiphenylene or bisphenols in the
broadest sense of the term, such as bis(hydroxyphenyl)alkanes,
cycloalkanes, sulfides, ethers, ketones, sulfones, sulfoxides,
.alpha.,.alpha.'-bis(hydroxyphenyl- )-diisopropylbenzenes, for
example the compounds 2,2-bis(4-hydroxyphenyl)p- ropane,
2,2-bis(3,5-dimethyl-4-hydroxyphenyl)-propane,
2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane,
1,1-bis(4-hydroxyphenyl)cyc- lohexane, or from the compounds of the
formulae: 24
[0294] In one embodiment, the preferred resins are polycarbonates
based on dihydric phenols such as 2,2-bis-(4-hydroxyphenyl)propane
(bisphenol A); 2,4-bis (4-hydroxyphenyl)-2-methylbutane;
1,1-bis-(4-hydroxyphenyl)-cyclo- hexane;
2,2-bis-(3-chloro-4-hydroxyphenyl)propane; 4,4'-sulfonyldiphenol;
and 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.
[0295] Also preferred are polycarbonate copolymers incorporating
two or more phenols, branched polycarbonates wherein a
polyfunctional aromatic compounds is reacted with the dihydric
phenol(s) and carbonate precursor, and polymer blends of which
polycarbonate comprises a significant portion of the blend.
[0296] The most preferred resins for both layers are polycarbonates
based on bisphenol A.
[0297] U.S. Pat. No. 5,288,788 also describes polycarbonates and
polyester carbonates, especially aromatic polycarbonates, for
example those based on 2,2-bis(4-hydroxyphenyl)propane or
1,1-bis(4-hydroxyphenyl)cyclohexane- .
MULTILAYER SYSTEMS
[0298] British Patent Application No. 2,290,745 describes a number
of methods have been developed to concentrate UV absorbers near or
at the surface of polymeric materials. These include surface
impregnation (see U.S. Pat. Nos. 3,309,220, 3,043,709, 4,481,664
and 4,937,026) and coating a plastic article with solutions
containing thermoplastic resins and UV absorbers (see U.S. Pat.
Nos. 4,668,588 and 4,353,965). Both techniques suffer from
drawbacks including requiring additional processing steps (i.e.
applying, drying or curing), and encounter difficulties associated
with the handling of large processed articles. An additional
drawback, particularly relevant to polycarbonate sheet production,
is the detrimental effect such post addition treatment would have
on the surface of the polymeric substrate.
[0299] As described in the U.S. Pat. No. 5,445,872, application of
surface layers via coextrusion takes place in a known manner in
known coextrusion equipment as taught in U.S. Pat. Nos. 3,487,505
and 3,557,265. Coextrusion is a well recognized method of producing
laminated thermoplastic materials by simultaneously extruding
various numbers of layers which form a single composite material.
U.S. Pat. No. 4,540,623 describes coextruded materials of at least
forty layers. Other methods produce as few as two or three
different layers.
[0300] In one embodiment, the invention also relates to
thermoplastic articles coated with a thermoplastic layer 0.1 to 10
mil (0.00254 mm to 0.254 mm), preferable 0.1 to 5 mil (0.00254 mm
to 0.127 mm), thick, in which said layer contains 0.1% to 20% by
weight of the benzocyclie-substituted pyrimidines and triazines of
the present invention. Preferred concentrations of are 2% to 15% by
weight; most preferred concentrations of 5% to 10% by weight.
[0301] The benzocycle-substituted pyrimidines and triazines of the
present invention may be incorporated into the thermoplastics of
the surfaces layer by standard methods such as dry mixing the
additives with granular resin prior to extruding.
[0302] The benzocycle-substituted pyrimidine or triazine layer may
be applied to one or both sides of the thermoplastic article.
[0303] Laminated thermoplastic articles which contain additional
layers such as a water resistant layer as found in U.S. Pat. No.
4,992,322 are also part of the present invention.
[0304] The core layer and the coating layer may be the same or
different thermoplastic resin including polyesters, polyester
carbonates, polyphenylene oxide, polyvinyl chloride, polypropylene,
polypropylene, polyethylene, polyacrylates, polymethacrylates and
copolymers and blends such as styrene and acrylonitrile on
polybutadiene and styrene with maleic anhydride, and mixtures
(polyblends) of such polymers with one another or with other
polymers, for example with polyolefins, polyacrylates, polydienes
or other elastomers in the form of impact strength modifiers.
BONDABLE STABILIZERS
[0305] The benzocycle-substituted pyrimidines and triazines of the
present invention can also be chemically bonded to substrates, such
as polymers, thereby greatly reducing the migration of such UV
absorbers, e.g., out of the substrate or away from the substrate
surface. The bonding mechanism of the triazines of the present
invention involves the formation of a bond (chemical and/or
co-valent) between a functionality attached to the amido or
carbamate group, e.g., by a pendant vinyl or hydroxyl group, and
the "host" substrate, such as a polymer.
[0306] Incorporation of the benzocycle-substituted pyrimidines and
triazines of the invention can be brought about by
copolymerization, copolyaddition, copolycondensation, by reaction
with a polymer which carries suitable functional groups, or by
grafting, in a manner as disclosed in U.S. Pat. Nos. 3,423,360 and
5,189,084 which are incorporated herein by reference as if filly
set forth.
[0307] Bonding of the benzocycle-substituted pyrimidines and
triazines of the invention can occur by polymerization or
copolymerization. In the case of the novel triazines of the present
invention comprising pendant vinyl groups, polymerization or
copolymerization with at least one vinyl monomer, e.g.,
(meth)acrylic acid, esters of (meth)acrylic acid such as methyl
acrylate, amides of (meth)acrylic acid, hydroxyethylacrylate,
olefins, vinyl chloride, styrene, butadiene, isoprene and
acrylonitrile can be carried out to form homopolymers or copolymers
in which the vinyl group is incorporated into the backbone of the
polymer. Polymerization or copolymerization can be initiated by
initiators, such as free radical, anionic and cationic types, or by
actinic radiation, such as UV, electron beam, x-rays and gamma
irradiation from a Co.sup.60 source, as is well known to those in
the polymerization art. Polymerization or copolymerization can be
carried out in solution, in an emulsion, in a dispersion, in the
melt, or in the solid state as is well known to those in the
polymerization art.
[0308] Also, bonding of the presently claimed
benzocycle-substituted pyrimidines and triazines compounds of the
present invention can be brought about by copolyaddition or
copolycondensation. Such incorporation can be made by addition
during the synthesis of an addition polymer or copolymer or by
condensation during the synthesis of a condensation polymer or
copolymer by methods known to those skilled in the art. For
example, compounds of the formula (I), (II), or (IV)-(IX)
containing the appropriate functional groups can be incorporated
into polyesters, polyamides, polyurethanes, epoxy resins, melamine
resins, alkyd resins, phenolic resins, polyurethanes,
polycarbonates, polysiloxanes, polyacetals and polyanhydrides, to
name but a few.
[0309] In addition, compounds of the formula (I), (II), or
(IV)-(IX) can be bonded to a monomeric component which is then
incorporated into a polymer or copolymer, e.g., by the free radical
initiated addition or copolycondensation methods described above.
Analogous methods are disclosed in, for example, U.S. Pat. No.
5,459,222 (incorporated by reference herein for all purposes as if
fully set forth) for the bonding of benzotriazole and benzophenone
stabilizers to diol precursors which are then incorporated by
condensation polymerization into polyurethanes and polyesters to
impart UV stabilizing properties to said polymers.
[0310] Alternately, the benzocycle-substituted pyrimidines and
triazines of the invention may also be bonded to polymers by
reaction with an oligomer and/or polymer which carries suitable
functional groups. For example, at least one triazine compound
comprising a vinyl pendant group can be added, optionally with at
least one other vinyl monomer or compound comprising -a vinyl
group, to unsaturated polyester resins, unsaturated polybutadiene
oligomers or unsaturated rubbers and then cured by actinic
radiation or by a free radical catalyst. Or, at least one triazine
compound comprising a terminal functional group, such as hydroxyl
or amido, may be reacted with a polymer and/or oligomer such as
polyesters, polyurethanes and polydiols with reactive end-groups,
partially hydrolyzed polyvinylacetate, epoxy resins, polysiloxanes
and polymers comprising maleic anhydride, either in the main chain
or as a side-chain, by methods analogous to those well known to
those of ordinary skill in the art.
[0311] Grafting is yet another way of bonding of the presently
claimed benzocycle-substituted pyrimidines and triazines to
polymers and/or oligomers. Grafting may be carried out in solution,
in the melt, or in the solid state with the initiators or actinic
radiation types discussed above for polymerization when, for
example, the novel triazines of the present invention comprising
pendant vinyl groups are used. Such benzocycle-substituted
pyrimidines and triazines may be grafted to saturated polymers,
e.g., polyolefins and their copolymers such as polyethylene,
polypropylene and poly(ethylene-vinyl acetate), or to polymers
comprising unsaturated moieties, e.g., polybutadiene, polyisoprene,
ethylene-propylene-(diene monomer) terpolymers and polystyrene and
its copolymers.
[0312] The benzocycle-substituted pyrimidines and triazines of the
present invention may be used in widely varying amounts in such
applications depending upon such things as the material to be
stabilized and the particular application. However, when employed
as a stabilizing additive for materials such as organic polymers,
the benzocycle-substituted pyrimidines and triazines of the present
invention are typically employed in amounts from about 0.01 to
about 20% by weight, preferably from about 0.1 to about 10% by
weight, and most preferably from about 0.1 to about 5% by weight,
based on the weight of the material to be stabilized. In screening
applications such as sunscreening compositions, the triazines are
utilized in the same relative amounts but based on the total weight
of the screening agent.
[0313] The novel stabilizers of the present invention may also be
employed in a non-bondable capacity, for example, in the
stabilization of thermoplastic polymers as set forth in the many of
the previously incorporated references. Examples of preferred
thermoplastic polymers are polyolefins and polymers comprising
heteroatoms in the main chain. Preferred polymers are also
thermoplastic polymers comprising nitrogen, oxygen and/or sulphur,
especially nitrogen or oxygen, in the main chain. Also of interest
are compositions in which the polymer is a polyolefin, for example
polyethylene or polypropylene.
[0314] Incorporation into the thermoplastic polymers can be carried
out by addition of the novel benzocycle-substituted triazine or
pyrimidine compound and any further additives by the methods
conventional in the art. The incorporation can expediently be made
before or during shaping, for example by mixing the pulverulent
components or by adding the stabilizer to the melt or solution of
the polymer, or by applying the dissolved or dispersed compounds to
the polymer, with or without subsequent evaporation of the solvent.
Elastomers can also be stabilized as lattices.
[0315] The novel mixtures can also be added to the polymers to be
stabilized in the form of a masterbatch which comprises these
compounds, for example, in a concentration of from about 2.5 to
about 25%, preferably from about 5 to about 20% by weight of the
polymer.
[0316] The novel mixtures can expediently be incorporated into the
polymeric material by any number of methods, including those
conventionally employed in the art, including by, for example: a)
as an emulsion or dispersion (for example to lattices or emulsion
polymers); (b) as a dry mix during mixing of additional components
or polymer mixtures; (c) by direct addition to the processing
equipment (for example extruders, internal mixers, etc.); or (d) as
a solution or melt.
[0317] The stabilized polymer compositions obtained in this way can
be converted into shaped articles, for example fibers, films,
tapes, sheets, sandwich boards, containers, pipes and other
profiles, by any number of conventional methods, for example hot
pressing, spinning, extrusion, roto-molding or injection molding.
Therefore, the present invention additionally relates to the use of
the polymer composition according to the invention for the
production of a shaped article.
[0318] Depending upon their ultimate end use, the
benzocycle-substituted pyrimidines and triazines of the present
invention may be combined with a variety of additives
conventionally employed in the UV stabilizing art. Examples of such
additives include but are not limited to:
[0319] a. Antioxidants
[0320] i) Alkylated monophenols such as
2,6di-tert-butyl-4-methylphenol; 2-tert-butyl-4,6-dimethylphenol;
2,6-di-tert-butyl-4-ethylphenol; 2,6-di-tert-butyl-4-n-butylphenol;
2,6-di-tert-butyl-4-isobutylphenol;
2,6-dicyclopentyl-4-methylphenol;
2-(.alpha.-methylcyclohexyl)-4,6-dimeth- ylphenol;
2,6-dioctadecyl-4-methylphenol; 2,4,6-tricyclohexylphenol;
2,6-di-tert-butyl-4-methoxymethylphenol; nonylphenols which are
liner or branched in the side chains such as
2,6-di-nonyl-4-methylphenol;
2,4-dimethyl-6-(1-methylundec-1-yl)phenol;
2,4-dimethyl-6-(1-methylheptad- ec-1-yl)phenol;
2,4-dimethyl-6-(1-methyltridec-1-yl)phenol; and mixtures
thereof.
[0321] (ii) Alkylthiomethylphenols such as
2,4-dioctylthiomethyl-6-tert-bu- tylphenol;
2,4-dioctylthiomethyl-6-methylphenol; 2,4-dioctylthiomethyl-6-e-
thylphenol; and 2,6-di-dodecylthiomethyl-4-nonylphenol.
[0322] (iii) Hydroquinones and alkylated hydroquinones such as
2,6-di-tert-butyl-4-methoxyphenol; 2,5-di-tert-butylhydroquinone;
2,5-di-tert-amylhydroquinone; 2,6-diphenyl-4-octadecyloxyphenol;
2,6-di-tert-butylhydroquinone; 2,5-di-tert-butyl-4-hydroxyanisole;
3,5-di-tert-butyl-4-hydroxyanisole;
3,5-di-tert-butyl-4-hydroxyphenyl stearate; and
bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.
[0323] (iv) Tocopherols such as .alpha.-tocopherol,
.beta.-tocopherol, .gamma.-tocopherol, .delta.-tocopherol, and
mixtures thereof (vitamin E).
[0324] (v) Hydroxylated thiodiphenyl ethers such as
2,2'-thiobis(6-tert-butyl-4-methylphenol);
2,2'-thiobis(4-octylphenol);
4,4'-thiobis(6-tert-butyl-3-methylphenol);
4,4'-thiobis(6-tert-butyl-2-me- thylphenol);
4,4'-thiobis(3,6-di-sec-amylphenol); and
4,4'-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.
[0325] (vi) Alkylidenebisphenols such as
2,2'-methylenebis(6-tert-butyl-4-- methylphenol);
2,2'-methylenebis(6-tert-butyl-4-ethylphenol);
2,2'-methylenebis[4-methyl-6-(.alpha.-methylcyclohexyl)phenol];
2,2'-methylenebis(4-methyl-6-cyclohexylphenol);
2,2'-methylenebis(6-nonyl- -4-methylphenol);
2,2'-methylenebis(4,6-di-tert-butylphenol);
2,2'-ethylidenebis(4,6-di-tert-butylphenol);
2,2'-ethylidenebis(6-tert-bu- tyl-4-isobutylphenol);
2,2'-methylenebis[6-(.alpha.-methylbenzyl)-4-nonylp- henol];
2,2'-methylenebis[6-(.alpha.,.alpha.-dimethylbenzyl)-4-nonylphenol-
]; 4,4'-methylenebis(2,6-di-tert-butylphenol);
4,4'-methylenebis(6-tert-bu- tyl-2-methylphenol);
1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane;
2,6-bis(3-tert-butyl-5-methyl-2-hydroxylbenzyl)-4-methylphenol;
1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane;
1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane;
ethylene glycol
bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate],
bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene;
bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphe-
nyl]terephthalate; 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane;
2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane;
2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane;
and
1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
[0326] (vii) O-, N- and S-benzyl compounds such as
3,5,3',5'-tetra-tert-bu- tyl-4,4'-dihydroxydibenzyl ether;
octadecyl-4-hydroxy-3,5-dimethylbenzylme- rcaptoacetate;
tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate;
tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine;
bis(4-tert-butyl-3-hydroxy--
2,6-dimethylbenzyl)dithioterephthalate;
bis(3,5-di-tert-butyl-4-hydroxyben- zyl)sulfide; and
isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate- .
[0327] (viii) Hydroxybenzylate malonates such as
dioctadecyl-2,2-bis(3,5-d- i-tert-butyl-2-hydroxybenzyl)malonate;
dioctadecyl-2-(3-tert-butyl-4-hydro- xy-5-methylbenzyl)malonate;
didodecylmercaptoethyl-2,2-bis(3,5-di-tert-but-
yl-4-hydroxybenzyl)malonate; and
bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2-
,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
[0328] (ix) Aromatic hydroxybenzyl compounds such as
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene;
1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene;
and 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
[0329] (x) Triazine compounds such as
2,4-bis(octylmercapto-6-(3,5-di-tert-
-butyl-4-hydroxyanilino)-1,3,5-triazine;
2-octylmercapto-4,6-bis(3,5-di-te-
rt-butyl-4-hydroxyanilino)-1,3,5-triazine;
2-octylmercapto-4,6-bis(3,5-di--
tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine;
2,4,6-tris(3,5-di-tert-butyl-- 4-hydroxyphenoxy)-1,3,5-triazine;
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybe- nzyl)isocyanurate;
1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)is-
ocyanurate;
2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triaz-
ine;
1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,-
5-triazine; and
1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.
[0330] (xi) Benzylphosphonates such as
dimethyl-2,5-di-tert-butyl-4-hydrox- ybenzylphosphonate;
diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate;
dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate;
dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate; and
the calcium salt of the monoethyl ester of
3,5-di-tert-butyl-4-hydroxybenzylp- hosphonic acid.
[0331] xii) Acylaminophenols such as 4-hydroxylauranilide;
4-hydroxystearanilide; and octyl
N-(3,5-di-tert-butyl-4-hydroxyphenyl)car- bamate.
[0332] xiii) Esters of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono-
or polyhydric alcohols such as methanol, ethanol, n-octanol,
i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene
glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane and
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.- 2]octane.
[0333] (xiv) Esters of
.beta.-(5-tert-butyl-4-hydroxy-3-methylphenyl)propi- onic acid with
mono- or polyhydric alcohols such as methanol, ethanol, n-octanol,
i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene
glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane and
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.- 2]octane.
[0334] (xv) Esters of
.beta.-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono-
or polyhydric alcohols such as methanol, ethanol, octanol,
octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,
1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)-oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane and
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0335] (xvi) Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic
acid with mono- or polyhydric alcohols such as methanol, ethanol,
octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene
glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl) isocyanurate, N,N'-bis-(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0336] (xvii) Amides of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propioni- c acid such as
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamet-
hylenediamine;
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimeth-
ylenediamine; and
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydr-
azine.
[0337] (xviii) Ascorbic acid (Vitamin C).
[0338] xix) Aminic antioxidants such as
N,N'-diisopropyl-p-phenylenediamin- e;
N,N'-di-sec-butyl-p-phenylenediamine;
N,N'-bis(1,4-dimethylpentyl)-p-ph- enylenediamine;
N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine;
N,N'-bis(1-methylheptyl)-p-phenylenediamine;
N,N'-dicyclohexyl-p-phenylen- ediamine;
N,N'-diphenyl-p-phenylenediamine; N,N'-bis(2-naphthyl)-p-phenyle-
nediamine; N-isopropyl-N'-phenyl-p-phenylenediamine;
N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine;
N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine;
N-cyclohexyl-N'-phenyl-p- -phenylenediamine;
4-(p-toluenesulfonamoyl)diphenylamine;
N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine; diphenylamine;
allyldiphenylamine;
4-isopropoxydiphenylamine,-phenyl-1-naphthylamine;
N-(4-tert-octylphenyl)-1-naphthylamine; N-phenyl-2-naphthylamine;
octylated diphenylamine such as p,p'-di-tert-octyldiphenylamine;
4-n-butylaminophenol; 4-butyrylaminophenol; 4-nonanoylaminophenol;
4-dodecanoylaminophenol; 4-octadecanoylaminophenol;
bis(4-methoxyphenyl)amine;
2,6-di-tert-butyl-4-dimethylaminomethylphenol;
2,4'-diaminophenylmethane; 4,4'-diaminodiphenylmethane;
N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane;
1,2-bis[(2-methylphenyl)amino]ethane; 1,2-bis(phenylamino)propane;
(o-tolyl)biguanide; bis[4-(1',3'-dimethylbutyl)phenyl]amine;
tert-octylated N-phenyl-1-naphthylamine; a mixture of mono- and
dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono-
and dialkylated nonyldiphenylamines; a mixture of mono- and
dialkylated dodecyldiphenylamines; a mixture of mono- and
dialkylated isopropyl/isohexyldiphenylamines, a mixture of mono-
and dialkylated tert-butyldiphenylamines;
2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine; phenothiazine; a
mixture of mono- and dialkylated tert-butyl/tert-octyl
phenothiazines; a mixture of mono- and dialkylated
tert-octylphenothiazines; N-allylphenothiazine;
N,N,N',N'-tetraphenyl-1,4- -diaminobut-2-ene;
N,N-bis(2,2,6,6-tetramethylpiperid-4-yl)hexamethylenedi- amine;
bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate;
2,2,6,6-tetramethylpiperidin-4-one; and
2,2,6,6-tetramethylpiperidin-4-ol- .
[0339] b. UV-absorbers and light stabilizers
[0340] (i) 2-(2'-Hydroxyphenyl)benzotriazoles such as
2-(2'-hydroxy-5'-methylphenyl)-benzotriazole;
2-(3',5'-di-tert-butyl-2'-h- ydroxyphenyl)benzotriazole;
2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazol- e;
2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole;
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole;
2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chloro-benzotriazole;
2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)-benzotriazole;
2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole;
2-(3',5'-di-tert-amyl-2'-hyd- roxphenyl)benzotriazole;
2-(3',5'-bis(.alpha.,.alpha.-dimethylbenzyl)-2'-h-
ydroxyphenyl)-benzotriazole; a mixture of
2-(3'-tert-butyl-2'-hydroxy-5'-(-
2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-
-5-chloro-benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonyl-
ethyl)phenyl)-5-chloro-benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-me-
thoxycarbonylethyl)phenyl)benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-
-octyloxycarbonylethyl)phenyl)benzotriazole,
2-(3'-tert-butyl-5'-[2-(2-eth-
ylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole,
2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole and
2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotri-
azole;
2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylph-
enol]; the transesterification product of
2-[3'-tert-butyl-5'-(2-methoxyca-
rbonylethyl)-2'-hydroxyphenyl]benzotriazole with polyethylene
glycol 300; and [R--CH.sub.2CH--COO(CH.sub.2).sub.3].sub.2 B where
R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl.
[0341] (ii) 2-Hydroxybenzophenones, 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 derivative.
[0342] (iii) Esters of substituted and unsubstituted benzoic acids
such as 4-tert-butyl-phenyl salicylate; phenyl salicylate;
octylphenyl salicylate; dibenzoyl resorcinol;
bis(4-tert-butylbenzoyl) resorcinol; benzoyl resorcinol;
2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybe- nzoate;
hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate; octadecyl
3,5-di-tert-butyl-4-hydroxybenzoate; and
2-methyl-4,6-di-tert-butylphenyl
3,5-di-tert-butyl-4-hydroxybenzoate.
[0343] (iv) Acrylates such as ethyl
.alpha.-cyano-.beta.,.beta.-diphenylac- rylate; isooctyl
.alpha.-cyano-.beta.,.beta.-diphenylacrylate; methyl
.alpha.-carbomethoxycinnamate; methyl
.alpha.-cyano-.beta.-methyl-p-metho- xycinnamate; butyl
.alpha.-cyano-.beta.-methyl-p-methoxycinnamate; methyl
.alpha.-carbomethoxy-p-methoxycinnamate; and
N-(.beta.-carbomethoxy-.beta- .-cyanovinyl)-2-methylindoline.
[0344] (v) Nickel compounds such as nickel complexes of
2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], including the
1:1 or 1:2 complex, with or without additional ligands such as
n-butylamine, triethanolamine or N-cyclohexyldiethanolamine; nickel
dibutyldithiocarbamate; nickel salts of monoalkyl esters including
the methyl or ethyl ester of
4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid; nickel complexes
of ketoximes including 2-hydroxy-4-methylphenyl undecyl ketoxime;
and nickel complexes of 1 -phenyl-4-lauroyl-5-hydroxypy- razole,
with or without additional ligands.
[0345] (vi) Sterically hindered amines as well as the N derivatives
thereof (e.g., N-alkyl, N-hydroxy, N-alkoxy and N-acyl), such as
bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate;
bis(2,2,6,6-tetramethylp- iperidin-4-yl)succinate;
bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate; bis(l
-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;
bis(1,2,2,6,6-pentamethylpiperidin-4-yl) n-butyl
3,5-di-tert-butyl-4-hydr- oxybenzylmalonate; the condensate of
1-(2-hydroxyethyl)-2,2,6,6-tetramethy- l-4-hydroxypiperidine and
succinic acid; the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-triazine;
tris(2,2,6,6-tetramethylpi- peridin4-yl) nitrilotriacetate;
tetrakis(2,2,6,6-tetramethylpiperidin-4-yl-
)-1,2,3,4-butanetetracarboxylate;
1,1'-(1,2-ethanediyl)bis(3,3,5,5-tetrame- thylpiperazinone);
4-benzoyl-2,2,6,6-tetramethylpiperidine;
4-stearyloxy-2,2,6,6-tetramethylpiperidine;
bis(1,2,2,6,6-pentamethylpipe-
ridyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate;
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate; the
condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and
4-morpholino-2,6-dichloro-1,3,5-triazine; the condensate of
2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triaz-
ine and 1,2-bis(3-aminopropylamino)ethane; the condensate of
2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-tri-
azine and 1,2-bis-(3- aminopropylamino)ethane;
8-acetyl-3-dodecyl-7,7,9,9-- tetramethyl-1,3,8-triazaspiro
[4.5]decane-2,4-dione;
3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione;
3-dodecyl-1-(1-ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5--
dione;
3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-di-
one; a mixture of 4-hexadecyloxy- and
4-stearyloxy-2,2,6,6-tetramethylpipe- ridine; the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexam- ethylenediamine
and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; the condensate
of 1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-tr-
iazine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.
[136504-96-6]);
2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[-
4.5]decane; oxo-piperanzinyl-triazines or so-called PIP-T HALS,
e.g., GOODRITE.RTM. 3034, 3150 and 3159 and similar materials
disclosed in U.S. Pat. No. 5,071,981; photobondable HALS such as
SANDUVOR.RTM. PR-31 and PR-32 (Clariant Corp.) and similar
materials disclosed in GB-A-2269819; and the reaction product of
7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8--
diaza-4-oxospiro[4.5]decane and epichlorohydrin. See also generally
U.S. Pat. No. 4,619,956, U.S. Pat. No. 5,106,891, GB-A-2269819,
EP-A-0309400, EP-A-0309401, EP-A-0309402 and EP-A-0434608.
[0346] (vii) Oxamides such as 4,4'-dioctyloxyoxanilide;
2,2'-diethoxyoxanilide; 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide;
2,2'-didodecyloxy-5,5'-di-tert-butyloxanilide;
2-ethoxy-2'-ethyloxanilide- ;
N,N'-bis(3-dimethylaminopropyl)oxamide;
2-ethoxy-5-tert-butyl-2'-ethylox- anilide and its mixture with
2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide; and mixtures of o- and
p-methoxy disubstituted oxanilides and mixtures of o- and p-ethoxy
disubstituted oxanilides.
[0347] (viii) 2-(2-Hydroxyphenyl)-1,3,5-triazines disclosed in the
previously incorporated references, such as
2,4,6-tris(2-hydroxy-4-octylo- xyphenyl)-1,3,5-triazine;
2-(2-hydroxy-4-n-octyloxyphenyl)-4,6-bis(2,4-dim-
ethylphenyl)-1,3,5-triazine; 2-(2-hydroxy-4-(mixed
iso-octyloxyphenyl)-4,6- -bis(2,4-dimethylphenyl)-1,3,5-triazine;
2-(2,4-dihydroxyphenyl)-4,6-bis(2-
,4-dimethylphenyl)-1,3,5-triazine;
2,4-bis(2-hydroxy-4-propyloxyphenyl)-6--
(2,4-dimethylphenyl)-1,3,5-triazine;
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bi-
s(4-methylphenyl)-1,3,5-triazine;
2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis-
(2,4-dimethylphenyl)-1,3,5-triazine;
2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-
-bis(2,4-dimethylphenyl)-1,3,5-triazine;
2-[2-hydroxy-4-(2-hydroxy-3-butyl-
oxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;
2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)-phenyl]-4,6-bis(2,4-dimeth-
ylphenyl)-1,3,5-triazine;
2-[4-dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2--
hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;
2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]4,6-bis(2,4-dimethyl-
phenyl)-1,3,5-triazine;
2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-- triazine;
2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine;
2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine;
and 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-
1,3,5-triazine.
[0348] (c) Metal deactivators such as N,N'-diphenyloxamide;
N-salicylal-N'-salicyloyl hydrazine; N,N'-bis(salicyloyl)hydrazine;
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine;
3-salicyloylamino-1,2,4-triazole; bis(benzylidene)oxalyl
dihydrazide; oxanilide; isophthaloyl dihydrazide; sebacoyl
bisphenylhydrazide; N,N'-diacetyladipoyl dihydrazide;
N,N'-bis(salicyloyl)oxalyl dihydrazide; and
N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
[0349] (d) Phosphites and phosphonites, such as triphenyl
phosphite; diphenyl alkyl phosphites; phenyl dialkyl phosphites;
tris(nonylphenyl) phosphite; trilauryl phosphite; trioctadecyl
phosphite; distearyl pentaerythritol diphosphite;
tris(2,4-di-tert-butylphenyl)phosphite; diisodecyl pentaerythritol
diphosphite; bis(2,4,-di-tert-butylphenyl)pent- aerythritol
diphosphite; bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythri- tol
diphosphite; bis(isodecyloxy)pentaerythritol diphosphite;
bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite;
bis(2,4,6-tris(tert-butyl)phenyl)pentaerythritol diphosphite;
tristearyl sorbitol triphosphite;
tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite;
6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1-
,3,2-dioxaphosphocin;
6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo-
[d,g]-1,3,2-dioxaphosphocin;
bis(2,4-di-tert-butyl-6-methylphenyl)methylph- osphite; and
bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite.
[0350] (e) Hydroxylamines such as 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; and
N,N-dialkylhydroxylamine derived from hydrogenated tallow fatty
amines.
[0351] (f) Nitrones such as 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-heptadecyl nitrone; N-hexadecyl-alpha-heptadecyl
nitrone; N-octadecyl-alpha-pentadec- yl nitrone;
N-heptadecyl-alpha-heptadecyl nitrone; N-octadecyl-alpha-hexad-
ecyl nitrone; and nitrones derived from N,N-dialkylhydroxylamines
prepared from hydrogenated tallow fatty amines.
[0352] (g) Thiosynergists such as dilauryl thiodipropionate and
distearyl thiodipropionate.
[0353] (h) Peroxide scavengers such as esters of
.beta.-thiodipropionic acid, for example the lauryl, stearyl,
myristyl or tridecyl esters; mercaptobenzimidazole or the zinc salt
of 2-mercaptobenzimidazole; zinc dibutyldithiocarbamate;
dioctadecyl disulfide; and pentaerythritol
tetrakis(.beta.-dodecylmercapto)propionate.
[0354] (i) Polyamide stabilizers such as copper salts in
combination with iodides and/or phosphorus compounds and salts of
divalent manganese.
[0355] (j) Basic co-stabilizers such as 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 calcium stearate, zinc stearate,
magnesium behenate, magnesium stearate, sodium ricinoleate and
potassium palmitate; antimony pyrocatecholate; and tin
pyrocatecholate.
[0356] (k) Nucleating agents including inorganic substances such as
talc and metal oxides (e.g. titanium oxide or magnesium oxide) and
phosphates, carbonates and sulfates of, preferably, alkaline earth
metals; organic compounds such as mono- or polycarboxylic acids and
salts thereof, for example 4-tert-butylbenzoic acid, adipic acid,
diphenylacetic acid, sodium succinate and sodium benzoate; and
polymeric compounds such as ionic copolymers (e.g., ionomers).
[0357] (l) Fillers and reinforcing agents such as calcium
carbonate; silicates; glass fibers; asbestos; talc; kaolin; mica;
barium sulfate; metal oxides and hydroxides; carbon black;
graphite; wood flour and flours or fibers from other natural
products; and synthetic fibers.
[0358] (m) Other additives such as plasticizers, lubricants,
emulsifiers, pigments, rheological additives, catalysts, levelling
assistants, optical brighteners, flameproofing agents, antistatic
agents and blowing agents.
[0359] (n) Benzofuranones and indolinones such as those disclosed
in U.S. Pat. No. 4,325,863, U.S. Pat. No. 4,338,244, U.S. Pat. No.
5,175,312, U.S. Pat. No. 5,216,052, U.S. Pat. No. 5,252,643,
DE-A-4316611, DE-A-4316622, DE-A-4316876, EP-A-0589839 and
EP-A-0591102;
3-[4-(2-acetoxy-ethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one;
5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)-phenyl]benzofuran-2-one;
3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one]-
; 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-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one;
and
5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one.
[0360] The novel benzocycle-substituted pyrimidines and triazines
of the present invention can also be employed in multilayer
systems. In such systems, a polymer composition having from about
0.1 to about 20% by weight and preferably a relatively high content
of novel stabilizer, for example, about 5-15% by weight, is applied
in a thin film (e.g., about 5-500 .mu.m thick and, preferably,
about 10-100 .mu.m thick) to a shaped article made from a polymer
containing little or no ultraviolet stabilizers. Such composition
may be applied at the same time as the shaping of the base
structure, for example by coextrusion in a manner analogous to that
described in U.S. Pat. No. 4,948,666 (incorporated by reference
herein for all purposes as if fully set forth). Alternatively,
application can also be made to the ready-formed base structure,
for example by lamination with a film or by coating with a
solution. The outer layer or layers of the finished article have
the function of a UV filter, which protects the interior of the
article from UV light. The outer layer preferably contains about
0.1 to about 20%, preferably about 1 to about 15%, and most
preferably about 2 to about 10% by weight of the outer layer
composition, of at least one of the benzocycle-substituted
pyrimidine or triazine compounds of the present invention.
[0361] The polymers stabilized in this way are notable for high
weathering resistance, especially for high resistance to UV light.
This enables them to retain their mechanical properties, and their
color surface properties such as gloss and distinctness of image,
for a long time even when used outside. Moreover, due to the
bondable nature of the presently claimed triazine compounds,
migration of these UV absorbers between the layers of the
multi-layer coatings can, under the appropriate circumstances, be
minimized.
[0362] In another embodiment of the present invention, the novel
mixtures comprising compounds of the formula (I), (II), or
(IV)-(IX) can be used as stabilizers for coatings, for example for
paints such as disclosed in numerous references (see, e.g., U.S.
Pat. No. 4,619,956, U.S. Pat. No. 4,740,542, U.S. Pat. No.
4,826,978, U.S. Pat. No. 4,962,142, U.S. Pat. No. 5,106,891, U.S.
Pat. No. 5,198,498, U.S. Pat. No. 5,298,067, U.S. Pat. No.
5,322,868, U.S. Pat. No. 5,354,794, U.S. Pat. No. 5,369,140, U.S.
Pat. No. 5,420,204, U.S. Pat. No. 5,461,151, U.S. Pat. No.
5,476,937, EP-0434608 and EP-A-0444323). Of particular interest are
coatings and paints for the automobile industry. The invention
therefore also relates to those compositions which are film-forming
binders for coatings.
[0363] Such novel coating compositions comprise about 0.01 to about
20%, preferably about 0.01 to about 10%, and more preferably about
0.02 to about 5% by weight of the binder of the coating composition
of the presently claimed benzocycle-substituted pyrimidines and
triazines of the present invention.
[0364] Multilayer systems are possible here as well (such as
electrocoat/basecoat/clearcoat systems), where the concentration of
the novel stabilizer in one or more of the layers, and typically
the outer layer such as the clearcoat, can be relatively high, for
example from about 0.01 to about 20%, preferably about 0.01 to
about 10%, and more preferably about 0.02 to about 5% by weight of
binder.
[0365] The use of the novel stabilizer in coatings is accompanied
by the additional advantage that it prevents delamination, i.e. the
flaking-off of the coating from the substrate. This advantage is
particularly important in the case of metallic substrates,
including multilayer systems on metallic substrates, and
particularly epoxy e-coated metallic substrates.
[0366] The binder can in principle be any binder which is customary
in industry, for example those described in Ullmann's Encyclopedia
of Industrial Chemistry, 5th Edition, Vol. A18, pp. 368-426, VCH,
Weinheim 1991 which is incorporated herein by reference. In
general, it is a film-forming binder based on a thermoplastic or
curable resin, predominantly on a curable resin. Examples of
thermoplastic binders include acrylics, polyesters, polyurethanes
and PVC plastisols. Examples of curable binders include functional
alkyd, acrylic, polyester, phenolic, melamine, epoxy and
polyurethane resins and mixtures thereof.
[0367] Such curable binders can be an ambient curable or a
thermosetting binder. Further, in some systems it may be
advantageous to add a curing catalyst to such systems. Suitable
catalysts which accelerate curing of the binder are described, for
example, in Ullmann's Encyclopedia of Industrial Chemistry, Vol.
A18, p. 469, VCH Verlagsgesellschaft, Weinheim 1991. Preferred
binders include those which comprise a functional acrylate resin
and a crosslinking agent.
[0368] A wide variety of binders may be employed in such coating
systems. Examples of suitable coating compositions containing
specific binders include but are not limited to:
[0369] 1. paints based on ambient curable or thermosetting alkyd,
acrylate, polyester, epoxy or melamine resins or mixtures of such
resins, if desired with addition of a curing catalyst;
[0370] 2. two-component polyurethane paints based on
hydroxyl-containing acrylate, polyester or polyether resins and
aliphatic or aromatic isocyanates, isocyanurates or
polyisocyanates;
[0371] 3. one-component polyurethane paints based on blocked
isocyanates, isocyanurates or polyisocyanates which are deblocked
during baking;
[0372] 4. two-component paints based on (poly)ketimines and
aliphatic or aromatic isocyanates, isocyanurates or
polyisocyanates;
[0373] 5. two-component paints based on (poly)ketimines and an
unsaturated acrylate resin or a polyacetoacetate resin or a
methacrylamidoglycolate methyl ester;
[0374] 6. two-component paints based on carboxyl- or
amino-containing polyacrylates and polyepoxides;
[0375] 7. two-component paints based on acrylate resins containing
anhydride groups and on a polyhydroxy or polyamino component;
[0376] 8. two-component paints based on (poly)oxazolines and
acrylate resins containing anhydride groups, or unsaturated
acrylate resins, or aliphatic or aromatic isocyanates,
isocyanurates or polyisocyanates;
[0377] 9. two-component paints based on unsaturated polyacrylates
and polymalonates;
[0378] 10. thermoplastic polyacrylate paints based on thermoplastic
acrylate resins or externally crosslinking acrylate resins in
combination with etherified melamine resins;
[0379] 11. paint systems based on siloxane-modified or
fluorine-modified acrylate resins.
[0380] In addition to the binder and novel benzocycle-substituted
pyrimidines and triazines of the present invention, the coating
composition according to the invention preferably further comprise
one or more additional ultraviolet light absorbers, including but
not limited to those specifically listed above in section b. The
additional UV absorbers may be, for example, another
tris-aryl-1,3,5-triazine, a 2-hydroxyphenyl-2H-benzotriazole, a
2-hydroxybenzophenone, an ester of an unsubstituted benzoic acid,
an acrylate, an oxamide (oxanilide), or any combination of the
above. Preferably, the additional UV absorber is a
2-hydroxyphenyl-2H-benzotriazole and the weight ratio of
benzotriazole to triazine is 4:1 to 1:4. More preferably, the
weight ratio is 2:1 to 1:2.
[0381] To achieve maximum light stability, it is of particular
interest to add sterically hindered amines, examples of which are
set out in the above-mentioned section b(vi). The invention
therefore also relates to a coating composition which, in addition
to the binder, the novel benzocycle-substituted pyrimidines and
triazines and, optionally, additional UV absorbers, comprises a
light stabilizer of the sterically hindered amine type. The
sterically hindered amine is employed in an amount of about 0.01 to
5% by weight based on the weight of the solid binder, preferably
about 0.02 to 2% by weight.
[0382] One specific example of such a sterically hindered amine is
a 2,2,6,6-tetramethyl piperazinone containing at least one group of
the formula: 25
[0383] in which J is, for example, hydrogen, hydroxyl, alkyl (such
as methyl), alkoxy (such as methoxy) or acyl.
[0384] More preferably the stabilizer is a
2,2,6,6-tetraalkylpiperidine derivative containing at least one
group of the formula: 26
[0385] in which J is, for example, hydrogen, hydroxyl, alkyl (such
as methyl), alkoxy (such as methoxy) or acyl.
[0386] Examples of tetraalkylpiperidine derivatives which can be
used in combination with the present trisaryl-1,3,5-triazine
compounds are given in U.S. Pat. Nos. 4,314,933, 4,344,876,
4,426,471, 4,426,472, 4,619,956, 5,004,770, 5,006,577, 5,064,883,
5,112,890, 5,124,378, 5,106,891, 5,204,473, and 5,461,151, which
are incorporated by reference herein for all purposes as if fully
set forth. It is particularly expedient to employ the following
tetraalkylpiperidine derivatives, as well as their N-alkyl, N-acyl,
N-hydroxyl and N-alkoxy analogs (where not already included in the
following list): bis(2,2,6,6-tetramethylpiperid-4-yl) succinate,
bis(2,2,6,6-tetramethylpiperid-4-yl) sebacate,
bis(1,2,2,6,6-pentamethylpiperid-4-yl) sebacate,
di(1,2,2,6,6-pentamethyl- piperid-4-yl)
butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,
bis(1-octyloxy-2,2,6,6-tetramethylpiperid-4-yl) sebacate,
tetra(2,2,6,6-tetramethylpiperid-4-yl) butane-
1,2,3,4-tetracarboxylate, tetra(1,2,2,6,6-pentamethylpiperid-4-yl)
butane-1,2,3,4-tetracarboxylate,
2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane,
and
8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2-
,4-dione. Commercially available examples of these and other
tetraalkylpipieridine derivatives include SANDUVOR.RTM. 3050, 3052,
3055, 3056, 3058, PR-31 and PR-32 (Clariant Corp.); TINUVIN.RTM.
079L, 123, 144, 292, 440L and 622LD (Ciba Specialty Chemicals);
CHIMASORB.RTM. 119 and 944 (Ciba Specialty Chemicals); and
CYASORB.RTM. UV-3346, UV 3529, UV-3853, UV-500 and UV-516 (Cytec
Industries Inc.).
[0387] Apart from the binder, the benzocycle-substituted pyrimidine
or triazine, and, if used, the additional ultraviolet light
absorber or stabilizer, the coating composition can also comprise
further components, examples being solvents, pigments, dyes,
plasticizers, stabilizers, thixotropic agents, drying catalysts
and/or leveling agents. Examples of possible components are those
described in many of the previously incorporated references as well
as Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition,
Vol. A18, pp. 429-471, VCH, Weinheim 1991; and Calbo, Leonard J.,
ed., Handbook of Coatings Additives, New York:Marcel Dekker
(1987).
[0388] Possible drying catalysts or curing catalysts are, for
example, organometallic compounds, amines, acids, amino-containing
resins and/or phosphines.
[0389] Examples of acid catalysts are mineral acids, aliphatic and
aromatic sulfonic acids (e.g. p-toluene sulfonic acid,
dinonylnaphthalene disulfonic acid, dodecylbenzene sulfonic acid),
oxalic acid, maleic acid, hexamic acid, phosphoric acid, alkyl
phosphate esters, phthalic acid and acrylic acid copolymers.
[0390] Examples of organometallic compounds are metal carboxylates,
especially those of the metals Pb, Mn, Co, Zn, Zr or Cu, or metal
chelates, especially those of the metal Al, It or Zr, or
organometallic compounds such as organotin compounds, for example.
Examples of metal carboxylates are the stearates of Pb, Mn or Zn,
the octoates of Co, Zn or Cu, the naphthenates of Mn and Co or the
corresponding linoleates, resinates or tallates. Examples of metal
chelates are the aluminum, titanium or zirconium chelates of
acetylacetone, ethyl acetylacetate, salicylaldehyde,
salicylaldoxime, o-hydroxyacetophenone or ethyl
trifluoroacetylacetate and the alkoxides of these metals. Examples
of organotin compounds are dibutyltin oxide, dibutyltin dilaurate
or dibutyltin dioctoate.
[0391] Examples of amine drying or curing catalysts are, in
particular, tertiary amines, for example tributylamine,
triethanolamine, N-methyldiethanolamine, N-dimethylethanolamine,
N-ethylmorpholine, N-methylmorpholine or diazabicyclooctane
(triethylenediamine) and salts thereof. Further examples are
quaternary ammonium salts, for example trimethylbenzylammonium
chloride. Amino-containing resins are simultaneously binder and
curing catalyst. Examples thereof are amino-containing acrylate
copolymers.
[0392] The curing catalyst used can also be a phosphine, for
example triphenylphosphine.
[0393] Another type of curing catalyst is a peroxide which can be
used, for example, to cure a gel coating for a fiberglass
article.
[0394] The novel coating compositions can also be radiation-curable
coating compositions. In this case, the binder essentially
comprises monomeric or oligomeric compounds containing
ethylenically unsaturated bonds, which after application are cured
by actinic radiation, i.e. converted into a crosslinked, high
molecular weight form. Where the system is UV-curing, it generally
contains a photoinitiator as well. Corresponding systems are
described in the above-mentioned publication Ullmann's Encyclopedia
of Industrial Chemistry, 5th Edition, Vol. A18, pages 451-453. In
radiation-curable coating compositions, the novel stabilizers can
also be employed without the addition of sterically hindered
amines.
[0395] The novel coating compositions according to the invention
can be applied to any desired substrates, for example to metal,
wood, plastic, fiberglass or ceramic materials. The coating
compositions can be pigmented mono-coats or multi-layer
(primer/basecoat/clearcoat) systems typical of automotive finishes.
In the latter case, the novel coating composition can be used for
either the base coat, or clear coat, or for both layers. If the
topcoat of an automotive finish comprises two layers, of which the
lower layer is pigmented and the upper layer is not pigmented, the
novel coating composition can be used for either the upper or the
lower layer or for both layers, but preferably for the upper
topcoat layer.
[0396] The novel coating compositions can be applied to the
substrates by the customary methods, for example by brushing,
spraying, pouring, dipping or electrophoresis; see also Ullmann's
Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp.
491-500.
[0397] Depending on the binder system, the coatings can be cured at
room temperature or by heating. Thermosetting coatings are
preferably cured at 50-150.degree. C. and, in the case of powder
coatings, even at higher temperatures.
[0398] The coatings obtained in accordance with the invention have
excellent resistance to the damaging effects of light, oxygen and
heat; particular mention should be made of the good light stability
and weathering resistance of the coatings thus obtained, for
example paints.
[0399] The invention therefore also relates to a coating, in
particular a paint, which has been stabilized against the damaging
effects of light, oxygen and heat by a content of the compound of
the formula (I), (II), or (IV)-(IX), according to the invention.
The paint can be a pigmented mono-coat which comprises a
film-forming binder and an organic pigment or dye, an inorganic
pigment, a metallic pigment, or a mixture thereof. The paint may
also be a composition which comprises a primer in adhesion to a
metal or plastic substrate; a pigmented basecoat that is in
adhesion to the primer and which comprises a film-forming binder
and an organic pigment or dye, an inorganic pigment, a metallic
pigment, or a mixture thereof; and a clear coat that is in adhesion
to the base coat and which comprises a film-forming binder and
optionally a transparent pigment. One especially preferred use is a
paint which is a clear topcoat for automobile original equipment
manufacture (OEM) and/or refinish applications.
[0400] The invention furthermore relates to a process for
stabilizing a coating based on polymers against damage by light,
oxygen and/or heat, which comprises mixing with the coating
composition a mixture comprising a compound of a
benzocycle-substituted pyrimidine or triazine and to the use of
mixtures comprising benzocycle-substituted pyrimidine or triazine
compound in coating compositions as stabilizers against damage by
light, oxygen and/or heat.
[0401] The coating compositions can comprise an organic solvent or
solvent mixture in which the binder is soluble. The coating
composition can otherwise be an aqueous solution or dispersion. The
vehicle can also be a mixture of organic solvent and water. The
coating composition maybe a high-solids paint or can be
solvent-free (e.g. a powder coating material).
[0402] The pigments can be inorganic, organic or metallic pigments.
The novel coating compositions preferably contain no pigments and
are used as a clearcoat.
[0403] Likewise preferred is the use of the coating composition as
a topcoat for applications in the automobile industry, especially
as a pigmented or unpigmented topcoat of the paint finish. Its use
for underlying coats, however, is also possible.
[0404] The benzocycle-substituted pyrimidine or triazines of this
invention may be applied topically by polishing a surface with a
composition comprising the benzocycle-substituted pyrimidine or
triazines and an inert carrier such as solvent, petroleum jelly,
silicone oil in water emulsions, or automotive paint wax, e.g.
Carnauba wax. These topical treatment compositions may be used to
stabilize coating films, fabrics, leather, vinyl and other plastics
and wood.
[0405] Preference is also given to the use of the novel
benzocycle-substituted pyrimidine or triazine compounds in
photographic materials as stabilizer against damage by light,
especially by UV light. The invention therefore also relates to a
photographic material comprising an benzocycle-substituted
pyrimidine or triazine compound.
[0406] The compounds according to the invention can be used for
photosensitive materials of all kinds. 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 other materials. They are preferably used, inter
alia, for photosensitive color material which comprises a reversal
substrate or which forms positives.
[0407] Furthermore, the novel compounds can be combined with other
UV absorbers, especially those which are dispersible in aqueous
gelatin, for example with hydroxyphenylbenzotriazoles (cf. for
example U.S. Pat. Nos. 4,853,471, 4,973,702, 4,921,966 and
4,973,701), benzophenones, oxanilides, cyanoacrylates, salicylates,
or acrylonitriles or thiazolines. In this context it is
advantageous to employ these further, oil-dissolved UV absorbers in
the photographic material in layers other than those comprising the
novel UV absorbers.
[0408] The present invention also encompasses compositions
containing one or more binders. In particular, the binder may
comprise an alkyd, acrylic, polyester, phenolic, melamine, epoxy or
polyurethane resin, or blends thereof. Examples of such binders
include, but are not limited to:
[0409] (a) cold- or hot-crosslinkable alkyd, acrylate, polyester,
epoxy or melamine resins or mixtures of such resins;
[0410] (b) a two-component polyurethane system comprising
hydroxyl-containing acrylate, polyester or polyether resins and
aliphatic or aromatic isocyanates, isocyanurates or
polyisocyanates;
[0411] (c) a one-component polyurethane system comprising blocked
isocyanates, isocyanurates or polyisocyanates which are deblocked
during baking;
[0412] (d) a two-component system comprising (poly)ketimines and
aliphatic or aromatic isocyanates, isocyanurates or
polyisocyanates;
[0413] (e) a two-component system comprising (poly)ketimines and an
unsaturated acrylate resin or a polyacetoacetate resin or a
methacrylamidoglycolate methyl ester;
[0414] (f) a two-component system comprising carboxyl- or
amino-containing polyacrylates and polyepoxides;
[0415] (g) a two-component system comprising acrylate resins
containing anhydride groups and on a polyhydroxy or polyamino
component;
[0416] (h) a two-component system comprising (poly)oxazolines and
acrylate resins containing anhydride groups, or unsaturated
acrylate resins, or aliphatic or aromatic isocyanates,
isocyanurates or polyisocyanates;
[0417] (i) a two-component system comprising unsaturated
polyacrylates and polymalonates;
[0418] (j) a thermoplastic polyacrylate system comprising
thermoplastic acrylate resins or externally crosslinking acrylate
resins in combination with etherified melamine resins; and
[0419] (k) a system comprising siloxane-modified or
fluorine-modified acrylate resins.
[0420] Such binder-containing compositions may further comprise a
curing catalyst, or an organic solvent, and may be
radiation-curable. In particular, such compositions may serve as
coating compositions.
[0421] In particular, it is possible successfully to stabilize
photographic materials similar to those described in U.S. Pat. No.
4,518,686.
[0422] The invention therefore additionally relates to a
photographic material comprising, on support, a blue-sensitive, a
green-sensitive and/or a red-sensitive silver-halide emulsion layer
and, if desired, a protective layer, with a layer comprising a UV
absorber being arranged above the uppermost silver-halide emulsion
layer, wherein the UV absorber is a benzocycle-substituted
pyrimidine or triazine compound.
[0423] Preference is additionally given to photographic materials
which have a layer comprising a compound of the formula (I), (II),
or (IV)-(IX) above the uppermost silver-halide emulsion layer
and/or between the green- and red-sensitive silver-halide emulsion
layers.
[0424] Furthermore, it may be advantageous for all or some of the
said layers which can comprise a UV absorber to have a UV absorber
mixture and/or a further UV absorber which is dispersible in
aqueous gelatin, but a compound of the formula (I), (II), or
(IV)-(IX) must be present at least in one layer.
[0425] The novel material preferably has gelatin interlayers
between the silver-halide emulsion layers.
[0426] Preference is given to photographic materials in which the
silver halide in the blue-sensitive, green-sensitive and/or
red-sensitive layer is silver chloride bromide comprising at least
90 mol % of silver chloride.
[0427] The compounds of the formula (I), (II), or (IV)-(IX), which
are used in accordance with the invention, can be incorporated,
alone or together with the color coupler and, if used, further
additives, into the color photographic materials by dissolving the
compounds beforehand in high-boiling organic solvents. It is
preferred to use solvents which boil at higher than 160.degree. C.
Typical examples of such solvents are the esters of phthalic acid,
phosphoric acid, citric acid, benzoic acid or of fatty acids, or
alkylamides and phenols.
[0428] Preferred color couplers for use in the compositions of the
invention, examples of such compounds, further additives such as
color cast inhibitors, DIR couplers and further light stabilizers,
such as UV absorbers, phenols, phosphorus (III) compounds,
organometallic complexes, hydroquinones and hydroquinone ethers,
and more precise details on the structure of various photographic
materials, can be found, for example, in the publications
EP-A-0531258 and EP-A-0520938 and in the literature cited
therein.
FILM
[0429] The invention also relates to a process for the
stabilization of polyolefin or polyolefin copolymer films for
agricultural applications, especially greenhouse applications, this
polyolefin or polyolefin copolymer film having improved light
stability and pesticide resistance, comprising incorporation of at
least one benzocycle-substituted pyrimidine or triazine UV
absorbers of the present invention, sterically hindered amines and
metal oxides of hydroxides selected from the oxides of zinc,
aluminum, calcium, and magnesium and hydroxides of zinc, aluminum,
and calcium into the polyolefin or polyolefin copolymer.
[0430] A further subject of the invention is a greenhouse,
characterized in that it is covered by a polyolefin or polyolefin
copolymer film having improved light stability and pesticide
resistance and stabilized with a at least one
benzocycle-substituted pyrimidine or triazine UV absorbers of the
present invention, sterically hindered amines and metal oxides of
hydroxides selected from the oxides of zinc, aluminum, calcium, and
magnesium and hydroxides of zinc, aluminum, and calcium.
[0431] Another subject of the invention is a process for
stabilizing a polyolefin or polyolefin copolymer greenhouse film
against detrimental effects of pesticides and light, oxygen and/or
heat, which process comprises incorporation of at least one
benzocycle-substituted pyrimidine or triazine UV absorbers of the
present invention, sterically hindered amines and metal oxides of
hydroxides selected from the oxides of zinc, aluminum, calcium, and
magnesium and hydroxides of zinc, aluminum, and calcium into said
greenhouse film.
[0432] Further subjects of the invention are the use of a
polyolefin copolymer film stabilized with at least one
benzocycle-substituted pyrimidine or triazine UV absorbers of the
present invention, sterically hindered amines and metal oxides of
hydroxides selected from the oxides of zinc, aluminum, calcium, and
magnesium and hydroxides of zinc, aluminum, and calcium for the
stabilization of polyolefin or polyolefin copolymer films in
contact with pesticides against photodegradation and damage by
pesticides.
[0433] To form a film, forcing a quantity of the said melted
composition through a film die, such as a flat film die or a
circular blown film die, and forming a film therefrom. In the case
where the composition is used to form a film therefrom, it is
contemplated that the films may be unoriented, or may be subjected
to a conventional operation to impart a degree of orientation on
the film. Such a film may be oriented in one direction, such as in
the machine direction, such as in the "machine direction" and/or
the "transverse direction", or may be oriented in both directions,
or "biaxially" oriented.
[0434] The present invention is also suitable for sheet
applications.
[0435] The benzocycle-substituted pyrimidine or triazine compounds
of the formula (I), (II), or (IV)-(IX) are suitable for the
photochemical stabilization of undyed, dyed or printed fiber
materials comprising for example, silk, leather, wool, polyamide or
polyurethanes and especially cellulose-containing fiber materials
of all kinds. Examples of such fiber materials are the natural
cellulose fibers, such as cotton, linen, jute and hemp and also
viscose staple fiber and regenerated cellulose. Preferred textile
fiber materials are those of cotton. The triazine and pyrimidine
compounds of the present invention are also suitable for the
photochemical stabilization of hydroxyl-containing fibers in blend
fabrics, for example blends of cotton with polyester fibers or
polyamide fibers. A further preferred area of application relates
to the blocking or reduction of the UV radiation which passes
through the above-mentioned textile materials (UV cutting) and the
heightened sun protection which textile materials finished with a
novel compound offer to the human skin.
[0436] To this end, one or a number of different compounds of the
formula (I), (II), or (IV)-(IX) are applied to the textile fiber
material by one of the customary dyeing methods, advantageously in
a quantity of 0.01 to 5% by weight, preferably 0.1 to 3% by weight
and, in particular, from 0.25 to 2% by weight, based on the weight
of the fiber material.
[0437] The benzocycle-substituted pyrimidine or triazine compounds
can be applied to the fiber material in various ways and fixed on
the fiber, especially in the form of aqueous dispersions or
printing pastes.
[0438] The textile fiber materials finished with the novel
compounds of the formula (I), (II), or (IV)-(IX) possess improved
protection against photochemical breakdown of the fiber and
yellowing phenomena and, in the case of dyed fibre material, are of
enhanced (hot) light fastness. Particular emphasis should be drawn
to the greatly improved photoprotective effect of the treated
textile fiber material and, in particular, the good protective
effect with respect to short-wave UV-B rays. This is manifested by
the fact that the textile fiber material finished with an
benzocycle-substituted pyrimidine or triazine compound has,
relative to untreated fabric, a greatly increased sun protection
factor (SPF).
[0439] The sun protection factor is defined as the quotient of the
dose of UV radiation which damages protected skin to that which
damages unprotected skin. Accordingly, a sun protection factor is
also a measure of the extent to which untreated fiber materials and
fiber materials treated with a novel compound of the formula (I),
(II), or (IV)-(IX) are permeable to UV radiation. The determination
of the sun protection factor of textile fiber materials is
explained, for example, in WO94/04515 or in J. Soc. Cosmet. Chem.
40, 127-133 (1989) and can be carried out analogously thereto.
[0440] Yet another use of the UV absorbers according to the
invention is in the stabilization of intra-ocular and contact
lenses.
[0441] The inventive UV absorbers are suitable as photoprotective
agents in cosmetic preparations. The invention additionally
relates, therefore, to a cosmetic preparation comprising at least
one benzocycle-substituted pyrimidine or triazine compound and
cosmetically acceptable carriers or auxiliaries.
[0442] The novel cosmetic composition contains from 0.1 to 15% by
weight, preferably from 0.5 to 10% by weight, based on the overall
weight of the composition, of a benzocycle-substituted pyrimidine
or triazine UV absorber and a cosmetically acceptable
auxiliary.
[0443] The cosmetic composition can be prepared by physically
mixing the novel UV absorber with the auxiliary by means of
customary methods, for example by simply stirring together the two
materials.
[0444] The cosmetic preparation according to the invention can be
formulated as a water-in-oil or oil-in-water emulsion, as an
oil-in-oil alcohol lotion, as a vesicular dispersion of an ionic or
nonionic amphiphilic lipid, as a gel, solid stick or as an aerosol
formulation.
[0445] As a water-in-oil or oil-in-water emulsion, the cosmetically
acceptable auxiliary preferably contains from 5 to 50% of an oily
phase, from 5 to 20% of an emulsifier and from 30 to 90% water. The
oil phase can comprise any oil which is suitable for cosmetic
formulations, e.g., one or more hydrocarbon oils, a wax, a natural
oil, a silicone oil, a fatty acid ester or a fatty alcohol.
Preferred mono- or polyols are ethanol, isopropanol, propylene
glycol, hexylene glycol, glycerol and sorbitol.
[0446] For these cosmetic formulations, it is possible to use any
conventionally employed emulsifier, e.g., one or more ethoxylated
esters of naturally occurring derivatives, i.e., polyethoxylated
esters of hydrogenated castor oil; or a silicone oil emulsifier
such as silicone polyol; an unmodified or ethoxylated fatty acid
soap; an ethoxylated fatty alcohol; an unmodified or ethoxylated
sorbitan ester; an ethoxylated fatty acid; or an ethoxylated
glyceride.
[0447] The cosmetic formulation can also comprise further
components, for example emollients, emulsion stabilizers, skin
moisteners, tanning accelerators, thickeners such as xanthan,
moisture retention agents such as glycerol, preservatives, or
fragrances and colorants.
[0448] The novel cosmetic formulations are notable for good
protection of human skin against the damaging effect of sunlight
while at the same time providing for reliable tanning of the
skin.
[0449] The invention will now be illustrated by the following
examples. The examples are not intended to be limiting of the scope
of the present invention. In conjunction with the general and
detailed descriptions above, the examples provide further
understanding of the present invention.
EXAMPLES
[0450] Examples and reaction schemes for producing specific
examples of benzocycle substituted triazines in accordance with the
invention are provided below. While the following examples
illustrate preparations with one or more tetralin benzocyles, one
of ordinary skill will understand that these reactions may also be
carried out with any of a variety of other benzocycles, where when
necessary, reactive substituents on such other benzocycles are
protected in accordance with procedures and reagents well known and
understood by those of ordinary skill.
PREPARATIVE EXAMPLES
Example 1: Reaction of Cyanuric Chloride with Tetralin: Use of
Tetralin as Solvent
[0451] 27
[0452] To a reaction flask equipped with a reflux condenser, an
argon inlet, a magnetic stirring bar and a glass stopper was added
100 mL of tetralin and 9.2 g of cyanuric chloride. To the resulting
solution was added 10 g of anhydrous AlCl.sub.3 over a period of 10
minutes at 0.degree. C. After the addition was over, the reaction
mixture was heated in an oil bath at 40.degree. C. for 16 hours.
The heating was discontinued and the reaction mixture was cooled in
an ice bath and treated with ice-cold water. The reaction mixture
was then extracted with methylene chloride and the organic layer
dried over anhydrous sodium sulfate and concentrated to remove
volatiles. The residue was treated with methanol affording a
precipitate which was filtered, washed with methanol and dried to
give 12.4 g of the product. The NMR and mass analysis of the
product showed it to consist of a mixture of
monotetralin-bischloro-triazine (Compound A),
bistetralin-monochloro-tria- zine (Compound B) and
tristetralin-triazine (Compound C).
Example 1 Alternate Procedure: Use of Monochlorobenzene as
Solvent
[0453] A mixture of 47.7 g (0.256 mole) of cyanuric chloride and
67.6 g (0.507 mol) of aluminum chloride in 360 mL of chlorobenzene
under nitrogen was heated to 40.degree. C. Tetralin (68 mL, 0.500
mole) was added over the course of two hr. During this time the
temperature increased to 50.degree. C. The temperature was
maintained at 50.degree. C. until an exotherm occurred.
[0454] After the exotherm had subsided, 200 mL of 10% aqueous HCl
was added drop-wise such that the temperature was maintained below
50.degree. C. The resulting mixture was filtered. The aqueous layer
from the filtrate was extracted with methylene chloride. The
combined organic layers were washed with water, dried over
anhydrous magnesium sulfate, and treated with activated carbon.
After filtration, the filtrate was concentrated in vacuo. The
residue was taken up in 300 mL of tetrahydrofuran, and cooled to
0.degree. C. The precipitate was removed by filtration. The
filtrate was concentrated in vacuo to give an oil which slowly
crystallized to a dark yellow to brown solid, which contained
P-4036 (50-70 area % by HPLC) plus tris-tetralin triazine and
unreacted cyanuric chloride.
Example 2: Bistetralin-monoresorcinol-triazine (Compound D)
[0455] 28
[0456] A mixture of 132.3 g of the product of Example I Alternate
Procedure (Compound B) and 38.7 g of resorcinol in 300 mL of
chlorobenzene was heated to 60.degree. C. Aluminum chloride (61.0
g) was added over a 2 hr. during which time the temperature
increased to 80.degree. C. The mixture has held at 80.degree. C.
for an additional 2 hr.
[0457] After cooling to 60.degree. C., the reaction mixture was
poured into 400 mL of ice water. The mixture was concentrated in
vacuo. The residue was triturated with 400 mL of water, and the
resulting slurry was filtered. The solid was air-dried and then
dried in vacuo. A Soxhlet extraction of the solid was done with
refluxing chloroform. A solid precipitated from the chloroform
extract. The solid was filtered, washed with cold chloroform, and
dried to give Compound D as a light yellow powder in >92% purity
by HPLC.
Example 2 Alternate Procedure
[0458] To a stirred suspension of 40 g cyanuric chloride in 544 mL
chlorobenzene maintained at ice bath temperature under nitrogen was
added 87 g of aluminum chloride. Concentrated hydrochloric acid
(4.34 mL) was added over 10 min during which the reaction
temperature was kept below 5.degree. C. The reaction mixture was
stirred at between about 0.degree. C. to about 5.degree. C. for an
additional 10 min, and then cooled to -10.degree. C. Tetralin (56
mL) was added at -10.degree. C. over 2 hr. The reaction mixture was
then stirred at -10.degree. C. for 2 hr, warmed to 0.degree. C.,
and stirred for 1 hr.
[0459] The reaction mixture was heated to 40.degree. C. and 26.3 g
of resorcinol was added over 10 min. The mixture was heated to
80.degree. C. and stirred for 2 hr. Compound D was isolated
according to the procedure of Example 3.
Example 3: Bistetralin-(monoresorcinol-4-O-octyl)-triazine
Derivative (Compound E)
[0460] 29
[0461] A mixture of 400 mg of the product of Example 2 (Compound
D), 1.38 g of anhydrous potassium carbonate, 0.2 mL of 1-iodooctane
and 10 mL of acetone was heated to reflux for 24 hours. The
reaction mixture was then cooled to room temperature and diluted
with methylene chloride. The resulting mixture was filtered through
Celite, and concentrated to dryness to give 422 mg of a crude
product. The crude product was purified by column chromatography
over silica gel to give a pure compound which was identified to be
the bistetralin-(monoresorcinol-4-O-octyl)-triazine derivative
(Compound E) by NMR and mass spectra.
Example 4: Monotetralin-bischloro-triazine (Compound F)
[0462] 30
[0463] A 3-necked, one liter flask was charged with 48 g of
anhydrous aluminum chloride, 56.11 g of cyanuric chloride and 240
mL of chlorobenzene. The apparatus was purged with nitrogen and the
mixture was heated to 65.degree. C.
[0464] Neat tetralin (60 mL) was added dropwise to the solution at
a constant rate of about 1.3 mL per minute such that all the
tetralin was added in 45 minutes. The temperature was maintained
between 63 and 68.degree. C. during this period. As the addition of
tetralin proceeded, the solution became red-black in color. After
the addition was complete, the temperature was maintained at
65-70.degree. C. for an additional 60 min. The mixture was then
allowed to cool to about 50.degree. C.
[0465] A mixture of 20 mL of concentrated aqueous HCl and 180 mL of
water was added through the dropping funnel. During the addition
the mixture was cooled with an ice bath. The aqueous acid was added
dropwise at least keeping the temperature between 45 and 50.degree.
C., and then more rapidly as the exothermic reaction lessened. The
entire mixture was diluted with 300 mL of methylene chloride, and
the aqueous layer was removed. The organic layer was washed twice
with water and then dried over anhydrous magnesium sulfate.
[0466] The dried organic mixture was then filtered to remove
magnesium sulfate and concentrated on a rotary evaporator. After
cooling, about 300 mL of hexanes was added giving a white
precipitate. This was filtered and washed with hexanes to give,
after drying in vacuo, the desired product (Compound F) in 96%
purity by HPLC analysis.
Example 5: Monotetralin-bisresorcinol-triazine (Compound G)
[0467] 31
[0468] To a 3-necked 250-mL round bottomed flask was charged with
14.0 g of monotetralin-bischloro-triazine (Compound F), 11.56 g of
resorcinol, and 130 mL of chlorobenzene and then purged with
nitrogen. Into the solids addition funnel was placed 18.76 g of
anhydrous aluminum chloride. The solution was heated to 49.degree.
C. and addition of aluminum chloride was begun in portions. The
aluminum chloride was added over the course of two hours and the
temperature allowed to slowly climb to 65.degree. C. The reaction
mixture was then heated to 90-95.degree. C. and held in that range
for 3 hours. The mixture was a dark red slurry at this point.
[0469] At the end of the reaction period, the heat was removed and
the temperature allowed to fall to about 60.degree. C. The
attachments were then removed from the reaction flask and the
mixture was poured into 200 mL of cold water. The mixture was
shaken, discharging the red color and leaving a yellow emulsion.
When this had cooled completely, it was transferred to a round
bottomed task and the chlorobenzene-water azeotrope was removed on
a rotary evaporator until no further chlorobenzene was observed in
the condensate. The resultant light yellow slurry was filtered,
washed with water and dried in vacuo to give the desired product
(Compound G).
Example 6: Preparation of Compounds H and I
[0470] 32
[0471] A mixture of 4.27 g of Compound G, 5.28 g of 1-iodooctane,
6.9 g of anhydrous potassium carbonate, 0.5 g of Aliquat 336 and 50
mL of acetone was heated to reflux for 20 hr. At this stage
additional 1 mL of 1-iodooctane and 3.5 g of anhydrous potassium
carbonate were added and the refluxing was continued for an
additional 8 hr. A TLC analysis at this stage showed almost
complete disappearance of Compound G and formation of two new
products. The reaction mixture was allowed to cool to room
temperature, diluted with methylene chloride and filtered through
Celite. The filtrate was concentrated under reduced pressure to
give a crude product which consisted of compounds H and I as
analyzed by NMR and mass spectra. The mixture is separable by
column chromatography over silica gel.
Example 7: Preparation of 4-(2-hydoxyethyl)ether of
Bis-Tetralin-mono-Resorcinol Triazine (Compound J)
[0472] 33
[0473] A mixture of 10.0 g of bis-tetralin-mono-resorcinol triazine
(Compound D), 130 mL of DMF, 2.6 g of anhydrous sodium carbonate,
0.25 g of potassium iodide, 0.88 g of PEG-400 (polyethylene
glycol), and 7.5 g of 2-chloroethanol was heated to 120.degree. C.
for 15 hr. After the first 9 hr. an additional 2.5 g of
2-chloroethanol was added and heating was continued. After
completion of the reaction, the mixture was poured into 300 mL of
ice water. The precipitated solids were filtered, washed with
water, and dried. HPLC and NMR analyses indicated that Compound J
was obtained in >90% purity.
Example 8: Preparation of 4-(6-hydroxyhexyl)ether of
Bis-Tetralin-mono-Resorcinol Triazine (Compound K)
[0474] 34
[0475] A mixture of 10 g of bis-tetralin-mono-resorcinol triazine
(Compound D, 0.02 mole) and 80 mL of MIBK was heated to 90.degree.
C. Sodium hydroxide 1.0 g (0.031 mole) was slowly added, resulting
in a nearly clear solution. Then 0.25 g (0.0015 mole) of potassium
iodide and 0.88 g of PEG-400 (polyethylene glycol, approx. 0.0022
mole) were added. After the solution again became clear, 5.7 g
(0.031 mole) of 6-chlorohexanol were added. The mixture was heated
at 107-111.degree. C. for 18 hr. The mixture was then washed with 1
N HCl and with water. The resulting solution was dried over
magnesium sulfate, filtered and cooled to 0.degree. C. The
resulting pale yellow solid was filtered, dried. HPLC and NMR
analyses indicated that the Compound K was obtained in >90%
purity.
Example 9: Preparation of 4-Lauroyl Ester Derivative of
Bis-Tetralin-mono-Resorcinol Triazine (Compound L)
[0476] 35
[0477] To a mixture of 20 g of Compound D and 80 mL of
ortho-dichlorobenzene were added 11.0 mL of lauroyl chloride
(Aldrich) and 10 mL of ortho-dichlorobenzene. The stirred mixture
was heated at 150.degree. C. for 9 hr. The mixture was then cooled
to 100.degree. C. and 200 mL of ethanol were added. The resulting
precipitate was filtered, washed with ethanol, and allowed to air
affording 21.3 g of Compound L as a pale yellow solid.
[0478] The solid was dissolved in 50 mL of hot toluene. The slurry
was warmed in a water bath until all of the solid dissolved.
Methanol (300 mL) was added to the mixture maintained at reflux
temperature. The solution was then cooled to room temperature. The
resulting solid was filtered, washed with several portions of
methanol, and dried in vacuo to give 20.25 g of the title compound
as a pale yellow solid.
Example 10: Preparation of 4-Hexanoyl Ester Derivative of
Bis-Tetralin-mono-Resorcinol Triazine (Compound M)
[0479] 36
[0480] To a mixture of 20 g of Compound D and 80 mL of
ortho-dichlorobenzene were added 8 mL of hexanoyl chloride
(Aldrich) and 10 mL of ortho-dichlorobenzene. The stirred mixture
was heated at 150.degree. C. for 12.5 hr. The product was isolated
by the procedure of Example 9 to give 14.1 g of the Compound M as a
pale yellow solid.
Example 11: Preparation of 4-Octanoyl Ester Derivative of
Bis-Tetralin-mono-Resorcinol Triazine (Compound N)
[0481] 37
[0482] To a mixture of 20 g of Compound D and 80 mL of
ortho-dichlorobenzene were added 8 mL of octanoyl chloride
(Aldrich) and 10 mL of ortho-dichlorobenzene. The stirred mixture
was heated at 150.degree. C. for 23.5 hr. The product was isolated
by the procedure of Example 2 to give 17.8 g of the Compound N as a
pale yellow solid.
Example 12: 4-(2-Ethylhexanoyl) Ester Derivative of
Bis-Tetralin-mono-Resorcinol Triazine (Compound O)
[0483] 38
[0484] To a mixture of 20 g of Compound D and 80 mL of
ortho-dichlorobenzene were added 8 mL of 2-ethylhexanoyl chloride
(Aldrich) and 10 mL of ortho-dichlorobenzene. The stirred mixture
was heated at 150.degree. C. for 20 hr. The mixture was then cooled
to 100.degree. C. and 200 mL of ethanol was added. Upon cooling to
0.degree. C. overnight an oil precipitated. The supernatant was
decanted off. The oil was dissolved in a refluxing hexanes-toluene
mixture, and then cooled to 0.degree. C. The resulting solid was
filtered, washed with methanol, and air dried to give 21.4 g of a
pale yellow solid. The solid was recrystallized from
hexanes-toluene, filtered, washed with methanol, and dried in vacuo
to give 15.8 g of Compound O as a pale yellow solid.
Example 13: 4-(3,5,5-trimethylhexanoyl) Ester Derivative of
Bis-Tetralin-mono-Resorcinol Triazine (Compound P)
[0485] 39
[0486] To a mixture of 20 g of Compound D and 80 mL of
ortho-dichlorobenzene were added 9 mL of 3,5,5-trimethylhexanoyl
chloride (Aldrich) and 10 mL of ortho-dichlorobenzene. The stirred
mixture was heated at 150.degree. C. for 7 hr. The mixture was then
cooled to 100.degree. C. and 200 mL of ethanol was added. Upon
cooling to 0.degree. C. overnight, an oil precipitated. The
supernatant was decanted off. The oil was washed with five 150 mL
portions of methanol and dried in vacuo. The resulting glass was
recrystallized twice from hexanes to give 13.1 g of the Compound P
as a pale yellow solid.
Example 14: Preparation of
2-(2-hydroxy-4-ethoxycarbonylmethoxyphenyl)-4,6-
-bis(tretralin)-1,3,5-triazine (Compound O)
[0487] 40
[0488] To a mixture of 9 g of Compound D, 6.9 g of anhydrous
potassium carbonate, 0.3 g of potassium iodide and 50 mL of acetone
was added 2.4 mL (2.7 g) of ethyl chloroacetate. The mixture was
stirred at reflux for six hours. HPLC analysis indicated full
conversion of Compound D. After cooling, the mixture was diluted
with 100 mL of methylene chloride and filtered through a bed of
diatomaceous earth, which was washed with an additional 50 mL of
methylene chloride. The combined filtrates were concentrated in
vacuo. The product was recrystallized from ethyl acetate and dried
in vacuo to give 8.4 g of Compound Q as a near white solid in 94%
purity (HPLC area % at 290 nm). The structure was verified by
.sup.13C and .sup.1H-NMR spectroscopy.
Example 15: Preparation of
2-[2-hydroxy-4-(N-(n-butyl)-N-(2-hydroxyethyl)--
methanamidooxy)phenyl]-4,6-bis(tetralin)-1,3,5-triazine) (Compound
R)
[0489] 41
[0490] A mixture of 5 g of Compound Q, 1.66 g of butyl
ethanolamine, 0.12 g of 4-dimethylaminopyridine, and 30 mL of
xylenes was stirred at reflux. After 26 hr, 2 g of butyl
ethanolamine was added. After 48 hr, HPLC analysis showed 99.5%
conversion of Compound P (area % at 290 nm). The mixture was
allowed to cool. The precipitated solids were diluted with 175 mL
of hexanes and stirred for 3 hr. The mixture was filtered and the
collected solid was air dried. The solid was stirred with 150 mL of
methanol for several hours, filtered, washed with methanol, and
dried in vacuo to give 5 g of Compound R as a white solid in 96%
purity (HPLC area % at 290 nm). The structure was verified by
.sup.13C and .sup.1H-NMR spectroscopy.
Example 16: Preparation of bis-tetralin-mono-resorcinol Triazine
4-O-propanesulfonate Ester (Compound S)
[0491] 42
[0492] To a stirred mixture of 11.6 g of Compound D, 9 g of
anhydrous potassium carbonate, and 100 mL of tetrahydrofuran (THF),
cooled to 4.degree. C. was added a solution of 3.15 mL of
propanesulfonyl chloride in 30 mL of THF over 22 min. The resulting
mixture was stirred for 40 hr at room temperature. An additional 1
mL of propanesulfonyl chloride was added, and the mixture was
stirred for 24 hr. HPLC analysis showed complete conversion of
starting material. The solids were removed by filtration and the
product was crystallized from the filtrate. The filtered solids
were extracted with chloroform, and the chloroform was removed in
vacuo to afford additional product. The combined yield was 8.5 g.
Recrystallization from ethyl acetate afforded Compound S in 99%
purity as determined by HPLC (area % at 290 nm). The structure was
verified by IR, .sup.13C, and .sup.1H-NMR spectroscopy.
Example 17: Preparation of bis-tetralin-mono-resorcinol triazine
4-O-phenylsulfonate Ester (Compound T)
[0493] 43
[0494] To a mixture of 15 g of Compound D, 13.8 g of anhydrous
potassium carbonate and 100 mL of tetrahydrofuran, cooled to
4.degree. C., was added a solution of 5.2 mL (7.1 g) of
benzenesulfonyl chloride in 30 mL of THF over 37 minutes. The
resulting mixture was allowed to warm to room temperature and
stirred for 19 hr. An additional 1 mL of benzenesulfonyl chloride
was added, and the mixture was stirred for 3 hr. Methanol (5 mL)
was added. The mixture was filtered, and the solids washed with
THF.
[0495] The product was crystallized from the combined filtrates,
filtered, and dried. Compound T (11.3 g) was obtained as a white
solid by recrystallization from chloroform/hexanes (1:3 v/v). HPLC
analysis showed 99% purity (area at 290 nm). The structure was
verified by .sup.13C and .sup.1H-NMR spectroscopy.
Example 18: Preparation of
Monotetralin-monoresorcinol-monochloro-1,3,5-tr- iazine (Compound
U)
[0496] 44
[0497] To a stirring mixture of 2.8 g of
monotetralin-bischloro-1,3,5-tria- zine (Compound F), 1 g of
resorcinol, and 25 mL of chlorobenzene was added 1.34 g of aluminum
chloride at ice-bath temperature. The reaction mixture was allowed
to warm to 15.degree. C. and stirred for 3 hr. The reaction mixture
was then allowed to warm to room temperature and stirred for 20 hr.
The reaction mixture was quenched with ice-cold 2% aqueous
hydrochloric acid. A precipitate formed, whcih was collected by
filtration, washed with water, and dried. The precipitate was
analyzed by thin layer chromatography (TLC), HPLC, and mass
spectroscopy, which identified Compound U as the major product.
Example 19: Preparation of a Hindered Phenol Adduct of
Bistetralin-monoresorcinol-1,3,5-triazine (Compound V)
[0498] 45
[0499] To a stirring mixture of 2.25 g of compound D, 2.76 g of
anhydrous potassium carbonate, and 50 mL of acetone was added 1.24
g of 3-chloromethyl-2,4-dimethyl-6-tert-butylphenol, 150 mg of
sodium iodide and 250 mg of Aliquat.RTM. 336
(triscaprylmethylammonium chloride). The reaction mixture was
heated to reflux for 3 hr. No starting material and only one major
product was detected using TLC and HPLC analysis. The reaction
mixture was allowed to cool to room temperature, diluted with 50 mL
of methylene chloride, and filtered through Celite.RTM. brand
filter agent. The filtrate was concentrated under reduced pressure.
The residue was dissolve in 100 mL of methylene chloride, washed
with water, dried over anhydrous sodium sulfate, and concentrated
to dryness to give Compound V, which was analyzed by mass
spectroscopy.
Example 20: Preparation of Hindered Phenol Adducts of
Monotetralin-bisresorcinol-1 3,5-triazine (Compounds W and X)
[0500] 46
[0501] To a stirring mixture of 2.14 g of Compound G, 5.5 g of
anhydrous potassium carbonate, and 40 mL of MIBK was added 2.49 g
of 3-chloromethyl-2,4-dimethyl-6-tert-butylphenol, 150 mg of sodium
iodide, and 250 mg of Aliquat.RTM. 336. The reaction mixture was
heated to reflux for 8 hr. After 8 hr, TLC analysis showed almost
no starting material. The reaction mixture was allowed to cool to
room temperature, diluted with methylene chloride, and filtered
through Celite.RTM. brand filter agent. The filtrate was
concentrated under reduce pressure, to give a mixture of Compounds
W and X as determined by TLC.
Example 21: Preparation of
2,4-bistetralin-6-(2,4-dihydroxy-3-diallylamino-
methyl)-1,3,5-triazine (Compound Y)
[0502] 47
[0503] To a stirring suspension of 2.2.5 g of Compound D in 50 mL
of toluene was added 3 mL of diallylamine and 5 mL of aqueous
formaldehyde. The reaction mixture was heated to reflux for 4 hr.
After 4 hr, TLC analysis detected almost no starting material and
the formation of one major product. The reaction mixture was
allowed to cool to room temperature and concentrated under reduced
pressure. The residue was dissolved in 100 mL of methylene
chloride, washed with water, dried over anhydrous sodium sulfate,
and concentrated under reduce pressure to give Compound X, which
was analyzed by mass spectroscopy.
Example 22: Preparation of
Bis-tetralin-mono-resorcinol-1,3,5-triazine Dimer (Compound Z)
[0504] 48
[0505] To a mixture of 10 g of Compound D, 12.2 g of anhydrous
potassium carbonate, 3.9 g of 1,5-diiodopentane, a catalytic amount
of Aliquat.RTM. 336, and 60 mL of dioxane was stirred at reflux for
24 hr. HPLC analysis indicated full conversion of compound D. After
cooling, the mixture was diluted with 150 mL of methylene chloride
and filtered through a bed of diatomaceous earth. The filtrate was
concentrated under reduced pressure to give compound U.
PERFORMANCE TESTING EXAMPLES
Example 23
[0506] 3% Toluene solutions of the stabilizers were prepared. The
colors of these solutions were measured in a 1-cm cell using a
Byk-Gardner Liquid Color Spectrophotometer. As can be seen from
Table 1, tetralin triazine UV absorbers Compound E and Compound J
have lower color than Tinuvin 1577, a current art triazine UV
absorber.
1TABLE I Color Values Of 3% Toluene Solutions Of Stabilizers
Stabilizer APHA Color Gardner Color CIE b value Tinuvin 1577 485 3
17.1 Compound B 364 2 13.2 Compound O 218 1 7.9
Example 24
[0507] Thermogravimetric analysis was carried out. Duplicate
specimens were heated in a Perkin-Elmer 7 Series thermobalance from
30-500.degree. C. at 10.degree. C./ min in both air. The purge gas
flow rate was .about.25 mL/min. Compound E was compared against the
major current art stabilizers for polycarbonate. As can be seen
from Table II, Compound E is significantly less volatile than
Tinuvin 1577, a current art stabilizer. (T-10% and T-20% are the
temperatures at which 10% and 20%, respectively, of weight loss
occurs during the above heating protocol.)
2TABLE II Thermogravimetric Data Stabilizer T-10% (.degree. C.)
T-20% (.degree. C.) Tinuvin 1577 346 363 Tinuvin 234 310 331
MixximBB/100 359 382 Compound B 419 440
Example 25
[0508] Polycarbonate plaques were prepared as follows. GE Lexan 105
barefoot natural flake polycarbonate resin (melt temperature
310-333.degree. C.) was dry blended with 0.35% stabilizer plus 0.10
wt % Mark.RTM. 2112 phosphite. The blended compositions were
melt-mixed and extruded in a Haake torque rheometer equipped with a
a 0.75-inch 25:1 single mixing screw extruder. The zone
temperatures were 246, 265, 295, and 304.degree. C. The extruded
polycarbonate was pulled through a water bath, dried, pelletized,
and redried at 120.degree. C. for 4-48 hr in a forced air oven. The
pellets were injection molded at 340.degree. C. with a 40 second
dwell time using an Arburg "Allrounder" hydraulic injection molder
to form 2.times.2.5.times.0.100-inch plaques. The mold temperature
was 100.degree. C. The injection barrel temperature of 340.degree.
C. was selected to simulate extremely harsh conditions. Yellow
indices and delta E data were obtained using a Macbeth Color Eye
Colorimeter with illuminate C, 2.degree. observer, specular
component excluded, and UV component included. As can be seen from
Table III, Compound E is more resistant to thermal yellowing than
Tinuvin 1577, a current art triazine UV absorber.
3TABLE III Color Of Stabilized Polycarbonate Plaques Injection
Molded At 340.degree. C. Stabilizer Yellow Index Tinuvin 1577 14.5
Compound E 11.9
Example 26
[0509] Stabilized polycarbonate plaques were prepared as in Example
3 with the exception that the injection molding temperatures were
lower. The temperatures were: nozzle-305.degree. C.; nozzle
side-310.degree. C.; middle-300.degree. C.; and feed-290.degree. C.
The plaques were subjected to 18 days of oven aging at 100.degree.
C. As can be seen from Table IV, Compound E inhibits thermal
yellowing of polycarbonate and has performance equal or better than
current art triazine UV absorbers Tinuvin 1577 and UV-1164.
4TABLE IV Oven Aging of Stabilized Polycarbonate Compositions at
100.degree. C. Stabilizer Delta E, 7 days Delta E, 18 days None 0.4
1.1 Compound B 0.5 0.4 Tinuvin 1577 0.5 0.5 UV-1164 0.4 0.6
Example 27
[0510] Stabilized polycarbonate plaques were prepared as in Example
4. They were exposed in a xenon-arc WeatherOmeter following ASTM
G-26 using Test Method B (Miami, Fla. conditions). The conditions
were an irradiance of 0.35 W/m.sup.2 at 340 nm, alternating cycles
of light and darkness, intermittent water spray, and a black panel
temperature of 63.+-.3.degree. C. Delta E (total color change) was
measured after 400 hr. of exposure. The results, summarized in
Table V show that Compound E is more effective in reducing total
color change than current art stabilizers Tinuvin 1577 and Tinuvin
234.
5TABLE V Accelerated Weathering of Stabilized Polycarbonate
Compositions Stabilizer Delta E None 5.3 Compound E 0.6 Tinuvin 234
0.9 Tinuvin 1577 1.0
Example 28: Stabilized Coating Compositions
[0511] Stabilized clear acrylic melamine compositions were prepared
and coated onto steel panels for accelerated weathering testing as
follows. Compound E (2% based on total resin solids) was
pre-dissolved in xylenes, alone and in combination with
Sanduvor.RTM. 3058 HALS (0.67% or 1.0% based on total resin
solids), and added to the clear acrylic melamine formulation given
in Table VI. Steel panels pre-coated with ED5050A E-coat, 764204
primer, and 542DF716 white base-coat and measuring 4".times.12"
were obtained from ACT Laboratories, Inc. (Hillsdale, Mich.). The
panels were coated with the clear coat formulations using the
draw-down technique (WC-52 Wire-Cators.TM. obtained from Leneta
Co., Ho-Ho-Kus, N.J.). The clear coats were allowed to flash for 10
min. at ambient temperature and cured for 30 min. at 135.degree.
C.
6TABLE VI Acrylic Melamine Clear Coat Formulation Material Amount
Doresco .RTM. TA 39-14 acrylic resin 81.25 g Cymel .RTM. 303
cross-linker 35.0 g Cycat .RTM. 4040 catalyst 1.0 g n-Butanol 20.0
g Xylene 16.0 g UV Absorber 0.364 g.sup.a Sanduvor .RTM. 3058.sup.b
0.182 g.sup.b .sup.a)Amount for 2% based on total resin solids
.sup.b)Amount for 1% based on total resin solids
[0512] Accelerated weathering is carried out with a QUV following
ASTM G53 (GM cycle), which is weathering under alternate cycles of
(i) UV light at 70 C. for 8 hours and (ii) condensation with no UV
light at 50 C. for 4 hr. Specular properties (gloss and
distinctness of image, or DOI) are measured as a function of
weathering time. Compositions containing either Compound E or
Compound J both have improved gloss and DOI retention relative to
the unstabilized control. Compositions containing HALS S-3058 in
addition to Compound E or Compound J also exhibit improved gloss
and DOI retention.
[0513] Although the present invention is described with reference
to certain preferred embodiments, it is apparent that modifications
and variations thereof may be made by those skilled in the art
without departing from the scope and spirit of this invention as
defined by the appended claims.
* * * * *