U.S. patent application number 09/848195 was filed with the patent office on 2001-11-01 for trisaryl-1,3,5-triazine ultraviolet light absorbers.
Invention is credited to Gupta, Ram Baboo, Haacke, Gottfried, Jakiela, Dennis John, Sassi, Thomas P..
Application Number | 20010037022 09/848195 |
Document ID | / |
Family ID | 22068984 |
Filed Date | 2001-11-01 |
United States Patent
Application |
20010037022 |
Kind Code |
A1 |
Gupta, Ram Baboo ; et
al. |
November 1, 2001 |
Trisaryl-1,3,5-triazine ultraviolet light absorbers
Abstract
This invention relates generally to amido or carbamate
substituted trisaryl-1,3,5-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
trisaryl-1,3,5-triazines comprises an aryl ring attached to the
triazine ring (and preferably an aryl ring containing a hydroxyl
group, either free or blocked to form a latent stabilizer, ortho-
to the point of attachment to the triazine ring) substituted with a
group comprising a bondable amido/carbamate containing group para-
to the point of attachment to the triazine 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 amido or carbamate substituted
trisaryl-1,3,5-triazines is also disclosed.
Inventors: |
Gupta, Ram Baboo; (Stamford,
CT) ; Jakiela, Dennis John; (Orange, CT) ;
Sassi, Thomas P.; (Stamford, CT) ; Haacke,
Gottfried; (New Canaan, CT) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION
PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
22068984 |
Appl. No.: |
09/848195 |
Filed: |
May 3, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09848195 |
May 3, 2001 |
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09197747 |
Nov 20, 1998 |
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6265576 |
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60066357 |
Nov 21, 1997 |
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Current U.S.
Class: |
544/215 |
Current CPC
Class: |
C07D 251/24 20130101;
C08K 5/3492 20130101 |
Class at
Publication: |
544/215 |
International
Class: |
C07D 253/065 |
Claims
What is claimed is:
1. A compound of the general formulas (I), (IA), (II) or (III):
30wherein each X is independently selected from hydrogen and a
blocking group; each of Y and Z is independently selected from an
aryl ring of the general formula (IV) 31each R is independently
selected from a hydrogen, a hydrocarbyl group and a functional
hydrocarbyl group; R' is selected from a divalent hydrocarbyl group
and a functional divalent hydrocarbyl group; each R.sup.1, R.sup.2,
R.sup.4, R.sup.4' and R.sup.4" is independently selected from
hydrogen, hydrocarbyl, functional hydrocarbyl, --O(hydrocarbyl),
--O(functional hydrocarbyl), --SR, halogen, --SO.sub.2R,
--SO.sub.3R, --COOR, --COR, --OCOR, --NRR and cyano; and each
R.sup.3 is independently selected from --R, --OR, --SR, halogen,
--SO.sub.2R, --SO.sub.3R, --COOR, --COR, --NRR and cyano;
characterized in that at least one R group of a 4-position --OR
group is selected from a group of the general formulas (V) ("amido
group") and (VI) ("carbamate group") 32wherein Q is selected from
NR.sup.10 and O; R.sup.5 is selected from a direct bond and a
hydrocarbylene group; R.sup.8 is a hydrocarbylene group; each
R.sup.6 and R.sup.7 is independently selected from a hydrocarbyl
group and a functional hydrocarbyl group, wherein at least one of
R.sup.6 and R.sup.7 is a functional hydrocarbyl group; or R.sup.6
and R.sup.7 taken together form a group selected from a functional
hydrocarbylene group, an unsaturated hydrocarbylene group and an
activated unsaturated hydrocarbylene group; each R.sup.9 is
selected from hydrogen, a hydrocarbyl group and a functional
hydrocarbyl group; and R.sup.10 is selected from hydrogen and a
hydrocarbyl group.
2. The compound of claim 1, wherein at least one R group of a
4-position --OR group is a group of the general formula V, and (i)
each of R.sup.6 and R.sup.7 is independently selected from a
hydrocarbyl group of 1 to 50 carbon atoms and a functional
hydrocarbyl group of 1 to 50 carbon atoms, with at least one of
R.sup.6 and R.sup.7 being such a functional hydrocarbyl group; or
(ii) R.sup.6 and R.sup.7 taken together form a group selected from
a functional hydrocarbylene group 3 to 24 carbon atoms, an
unsaturated hydrocarbylene group having 3 to 24 carbon atoms and an
activated unsaturated hydrocarbylene group having 3 to 24 carbon
atoms.
3. The compound of claim 2, wherein at least one of R.sup.6 and
R.sup.7 is a functional hydrocarbyl group possessing pendant and/or
terminal reactive and/or latent reactive functionality and/or
leaving groups.
4. The compound of claim 3, wherein R.sup.5 is --(CHR.sup.14)n-;
and R.sup.6 and R.sup.7 are each independently selected from the
group consisting of hydrogen, linear or branched alkyl of 1 to 24
carbon atoms, --(CH.sub.2).sub.nOH,
--(CH.sub.2)CH(OH)CH.sub.2OR.sup.15,
--(CH.sub.2)CH(OH)CH.sub.2R.sup.15 and 33
5. The compound of claim 4, wherein at least one of R.sup.6 and
R.sup.7 is a functional hydrocarbyl group possessing a pendant
and/or terminal group selected from the group consisting of
hydroxyl, --COOR.sup.11, --CR.sup.12.dbd.CH.sub.2,
--CO--CR.sup.12.dbd.CH.sub.2, --OCO--CR.sup.12.dbd.CH.sub.2,
--OCO--NH--R.sup.9, Cl, 34an isocyanate group, a blocked isocyanate
group and --NHR.sup.11, wherein R.sup.11 is selected from hydrogen
and a hydrocarbyl; and R.sup.12 is selected from hydrogen and an
alkyl of 1 to 4 carbon atoms.
6. The compound of claim 5, wherein at least one R group of a
4-position --OR group is a group selected from 35wherein n is 1-24,
n1 is 0-23, n2 is 1-24, n3 is 1-24, and R.sup.12 is selected from
hydrogen and an alkyl group of 1 to 4 carbon atoms.
7. The compound of claim 1, wherein at least one R of a 4-position
--OR group is a group of the general formula VI, and R.sup.9 is
selected from hydrogen, a hydrocarbyl group of 1 to 50 carbon atoms
and a functional hydrocarbyl group of 1 to 50 carbon atoms.
8. The compound of claim 7, wherein at least one R of a 4-position
--OR group is a group selected from 36wherein n is 1-24 and n1 is
0-23.
9. A compound according to claim 1, having the general formula
(VII), (VIII) or (IX): 37
10. The compound of claim 9, wherein at least one R group of a
4-position --OR group is a group of the general formula V, and (i)
each of R.sup.6 and R.sup.7 is independently selected from a
hydrocarbyl group of 1 to 50 carbon atoms and a functional
hydrocarbyl group of 1 to 50 carbon atoms, with at least one of
R.sup.6 and R.sup.7 being such a functional hydrocarbyl group; or
(ii) R.sup.6 and R.sup.7 taken together form a group selected from
a functional hydrocarbylene group 3 to 24 carbon atoms, an
unsaturated hydrocarbylene group having 3 to 24 carbon atoms and an
activated unsaturated hydrocarbylene group having 3 to 24 carbon
atoms.
11. The compound of claim 10, wherein at least one of R.sup.6 and
R.sup.7 is a functional hydrocarbyl group possessing pendant and/or
terminal reactive and/or latent reactive functionality and/or
leaving groups.
12. The compound of claim 10, wherein R.sup.5 is --(CHR.sup.14)n-;
and R.sup.6 and R.sup.7 are each independently selected from the
group consisting of hydrogen, linear or branched alkyl of 1 to 24
carbon atoms, --(CH.sub.2).sub.nOH, -- 38
13. The compound of claim 13, wherein at least one of R.sup.6 and
R.sup.7 is a functional hydrocarbyl group possessing a pendant
and/or terminal group selected from the group consisting of
hydroxyl, --COOR", --CR.sup.12.dbd.CH.sub.2,
--CO--CR.sup.12.dbd.CH.sub.2, --OCO--CR.sup.12.dbd.CH.sub.2,
--OCO--NH--R.sup.9, Cl, 39an isocyanate group, a blocked isocyanate
group and --NHR.sup.11, wherein R.sup.11 is selected from hydrogen
and a hydrocarbyl; and R.sup.12 is selected from hydrogen and an
alkyl of 1 to 4 carbon atoms.
14. The compound of claim 13, wherein at least one R group of a
4-position --OR group is a group selected from 40wherein n is 1-24,
n1 is 0-23, n2 is 1-24, n3 is 1-24, and R.sup.12 is selected from
hydrogen and an alkyl group of 1 to 4 carbon atoms.
15. The compound of claim 9, wherein at least one R of a 4-position
--OR group is a group of the general formula VI, and R.sup.9 is
selected from hydrogen, a hydrocarbyl group of 1 to 50 carbon atoms
and a functional hydrocarbyl group of 1 to 50 carbon atoms.
16. The compound of claim 15, wherein at least one R of a
4-position --OR group is a group selected from 41wherein n is 1-24
and n1 is 0-23.
17. A compound according to claim 1, having the general formula
(X), (XI) or (XII): 42
18. The compound of claim 17, wherein at least one R group of a
4-position --OR group is a group of the general formula V, and (i)
each of R.sup.6 and R.sup.7 is independently selected from a
hydrocarbyl group of 1 to 50 carbon atoms and a functional
hydrocarbyl group of 1 to 50 carbon atoms, with at least one of
R.sup.6 and R.sup.7 being such a functional hydrocarbyl group; or
(ii) R.sup.6 and R.sup.7 taken together form a group selected from
a functional hydrocarbylene group 3 to 24 carbon atoms, an
unsaturated hydrocarbylene group having 3 to 24 carbon atoms and an
activated unsaturated hydrocarbylene group having 3 to 24 carbon
atoms.
19. The compound of claim 18, wherein at least one of R.sup.6 and
R.sup.7 is a hydrocarbyl group containing a functional group
selected from the group comprising pendant, terminal reactive,
latent reactive functionality, or leaving groups.
20. The compound of claim 19, wherein R.sup.5 is --(CHR.sup.14)n-;
R.sup.6 and R.sup.7 are each independently selected from the group
consisting of hydrogen, linear or branched alkyl of 1 to 24 carbon
atoms, --(CH.sub.2).sub.nOH, --(CH.sub.2)CH(OH)CH.sub.2OR.sup.15,
43
21. The compound of claim 19, wherein at least one of R.sup.6 and
R.sup.7 is a functional hydrocarbyl group possessing a pendant
and/or terminal group selected from the group consisting of
hydroxyl, --COOR.sup.11, --CR.sup.12.dbd.CH.sub.2,
--CO--CR.sup.12--CH.sub.2, --OCO--CR.sup.12.dbd.CH.sub.2,
--OCO--NH--R.sup.9, Cl, 44an isocyanate group, a blocked isocyanate
group and --NHR.sup.11, wherein R.sup.11 is selected from hydrogen
and a hydrocarbyl; and R.sup.12 is selected from hydrogen and an
alkyl of 1 to 4 carbon atoms.
22. The compound of claim 21, wherein at least one R group of a
4-position --OR group is a group selected from 45wherein n is 1-24,
n1 is 0-23, n2 is 1-24, n3 is 1-24, and R.sup.12 is selected from
hydrogen and an alkyl group of 1 to 4 carbon atoms.
23. The compound of claim 17, wherein at least one R of a
4-position --OR group is a group of the general formula VI, and
R.sup.9 is selected from hydrogen, a hydrocarbyl group of 1 to 50
carbon atoms and a functional hydrocarbyl group of 1 to 50 carbon
atoms.
24. The compound of claim 23, wherein at least one R of a
4-position --OR group is a group selected from 46wherein n is 1-24
and n1 is 0-23.
25. A compound according to claim 1, having the general formula
(XIII): 47
26. A compound according to claim 1, having the general formula
(XIV): 48
27. A method of stabilizing a material which is subject to
degradation by actinic radiation 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 a compound as set forth in claim 1.
28. The method of claim 27, wherein the compound is incorporated in
an amount from about 0.01 to about 20% by weight based on the
weight of the material to be stabilized.
29. The method of claim 28, wherein the material to be stabilized
is an organic polymer.
30. The method of claim 29, wherein the compound is incorporated
into the organic polymer by chemical bonding during the preparation
of the organic polymer.
31. The method of claim 29, wherein the compound is incorporated
into the organic polymer by chemical bonding subsequent to the
preparation of the organic polymer.
32. A method of protecting a substrate against degradation by
actinic radiation by applying to the substrate a film 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 a
compound as set forth in claim 1.
33. A coating composition suitable for forming a film stabilized
against degradation by actinic radiation, comprising a film-forming
binder composition and an actinic radiation stabilizing amount of a
stabilizer composition, wherein the stabilizer composition
comprises a compound as set forth in claim 1.
34. The coating composition of claim 33, wherein the film-forming
binder is reactive with the compound under cure conditions.
35. A stabilized crosslinked film prepared by curing the coating
composition of claim 33.
36. The coating composition of claim 33, wherein the stabilizer
composition further comprises a hindered amine light
stabilizer.
37. The coating composition of claim 33, wherein the stabilizer
composition further comprises an ultraviolet light absorber other
than the compound.
38. The coating composition of claim 36, wherein the hindered amine
light stabilizer is a monomeric hindered amine light
stabilizer.
39. The coating composition of claim 37, wherein the ultraviolet
light absorber is a benzotriazole.
40. The coating composition of claim 37, wherein the ultraviolet
light absorber is 2-(2-hydroxyphenyl)-1,3,5-triazine.
41. The coating composition of claim 37, 39 or 40, further
comprising a hindered amine light stabilizer.
42. The coating composition of claim 41, wherein the hindered amine
light stabilizer is a monomeric hindered amine light stabilizer.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention relates generally to novel amido or carbamate
substituted trisaryl-1,3,5-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.
[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/or become brittle as a result
of prolonged 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 trisaryl-1,3,5-triazines, in which at least one of the aryl
rings has 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. Disclosures of a number of such trisaryl-1,3,5-triazines,
as well as processes for preparing and uses thereof, can be found
in the following publications, all of which are incorporated by
reference herein for all purposes as if fully set forth: U.S. Pat.
Nos. 3,118,887, 3,242,175, 3,244,708, 3,249,608, 3,268,474,
3,423,360, 3,444,164, 3,843,371, 4,619,956, 4,740,542, 4,775,707,
4,826,978, 4,831,068, 4,962,142, 5,030,731, 5,059,647, 5,071,981,
5,084,570, 4,831,068, 4,962,142, 5,030,731, 5,059,647, 5,071,981,
5,084,570, 5,106,891, 5,185,445, 5,189,084, 5,198,498, 5,288,778,
5,298,067, 5,300,414, 5,322,868, 5,354,794, 5,364,749, 5,369,140,
5,410,048, 5,412,008, 5,420,204, 5,461,151, 5,476,937, 5,478,935,
5,489,503, 5,543,518, 5,538,840, 5,545,836, 5,563,224, 5,575,958,
5,591,850, 5,597,854, GB1033387, CH480091, CH484695, EP-A-0434608,
EP-A-0532006, EP-A-0649841. EP-A-0693483, EP-A-0704560, WO95/05645,
WO95/22959 and WO96/28431.
[0006] 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.
This second 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"
trisaryl-1,3,5-triazines and the latter are referred to as
"bondable" trisaryl-1,3,5-triazines.
[0007] Many polymer additives (such as ultraviolet light
stabilizers) may suffer from a disadvantage that they volatilize or
migrate out of the polymer substrate to be protected, or that they
are adsorbed (chemically or physically) by one or more systems
components (such as pigments), thereby diminishing their
effectiveness.
[0008] 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, or between coatings and their plastic
substrates is greatly reduced.
[0009] Several of the previously incorporated references disclose
bondable trisaryl-1,3,5-triazines. For example, previously
incorporated U.S. Pat. Nos. 3,423,360, 4,962,142 and 5,189,084
disclose various bondable trisaryl-1,3,5-triazines and the
incorporation of these compounds into polymers by chemical bonding.
However, the inventors are unaware of any prior art which discloses
the novel amido or carbamate containing trisaryl-1,3,5-triazines of
the present invention.
SUMMARY OF THE INVENTION
[0010] The present invention provides a new class of bondable
trisaryl-1,3,5-triazines in which an aryl ring attached to the
triazine ring (and preferably an aryl ring containing a hydroxyl
group or "latent" hydroxyl group ortho- to the point of attachment
to the triazine ring) is substituted with a group comprising a
bondable amido/carbamate containing group para- to the point of
attachment to the triazine ring. More specifically, the new
trisaryl-1,3,5-triazines of the present invention have the
following general formulas (I), (IA), (II) and (III): 1
[0011] wherein each X is independently selected from hydrogen and a
blocking group;
[0012] each of Y and Z is independently selected from an aryl ring
of the general formula (IV) 2
[0013] each R is independently selected from a hydrogen, a
hydrocarbyl group and a functional hydrocarbyl group;
[0014] R' is selected from a divalent hydrocarbyl group and a
functional divalent hydrocarbyl group;
[0015] each R.sup.1, R.sup.2, R.sup.4, R.sup.4' and R.sup.4" is
independently selected from hydrogen, hydrocarbyl, functional
hydrocarbyl, --O(hydrocarbyl), --O(functional hydrocarbyl), --SR,
halogen, --SO.sub.2R, --SO.sub.3R, --COOR, --COR, --OCOR, --NRR and
cyano; and
[0016] each R.sup.3 is independently selected from --R, --OR, --SR,
halogen, --SO.sub.2R, --SO.sub.3R, --COOR, --COR, --NRR and
cyano;
[0017] characterized in that at least one R group of a 4-position
--OR group is selected from a group of the general formulas (V)
("amido group") and (VI) ("carbamate group") 3
[0018] wherein Q is selected from NR.sup.10 and O;
[0019] R.sup.5 is selected from a direct bond and a hydrocarbylene
group;
[0020] R.sup.8 is a hydrocarbylene group;
[0021] each R.sup.6 and R.sup.7 is independently selected from a
hydrocarbyl group and a functional hydrocarbyl group, wherein at
least one of R.sup.6 and R.sup.7 is a functional hydrocarbyl group;
or
[0022] R.sup.6 and R.sup.7 taken together form a group selected
from a functional hydrocarbylene group, an unsaturated
hydrocarbylene group and an activated unsaturated hydrocarbylene
group;
[0023] each R.sup.9 is selected from hydrogen, a hydrocarbyl group
and a functional hydrocarbyl group; and
[0024] R.sup.10 is selected from hydrogen and a hydrocarbyl
group.
[0025] The amido or carbamate containing tris-aryl-1,3,5-triazines
of the present invention have the added benefit of being capable of
being chemically bound to appropriate polymer systems via
functionality attached to the amido or carbamate group (e.g., by a
hydroxyl, ethylenic unsaturated and/or activated unsaturated group
in one or more of R.sup.6, R.sup.7 or R.sup.9) or, for a carbamate
(formula (VI)) containing triazine, by direct bonding via the
nitrogen atom of the carbamate group, especially if R.sup.9 is
hydrogen.
[0026] These trisaryl-1,3,5-triazines may in general be prepared
via a number of procedures described in the previously incorporated
references, but preferably by reacting a trisaryl-1,3,5-triazine
precursor, having at least one aryl ring with a hydroxyl group para
to the point of attachment to the triazine ring (and preferably
hydroxyl groups both ortho and para to the point of attachment to
the triazine ring), with an appropriate compound or compounds to
functionalize the para position hydroxyl with a group of the above
formula (V) or (VI). Further preferred process details are
disclosed below.
[0027] The novel amido or carbamate containing
trisaryl-1,3,5-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,
rubbers, paints and other coatings, and adhesives, such as
disclosed in a number of the previously incorporated references.
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 or shaped article) 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 amido or carbamate
containing trisaryl-1,3,5-triazine; and (2) the material so
stabilized.
[0028] The novel amido or carbamate containing
trisaryl-1,3,5-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 amido or carbamate containing
trisaryl-1,3,5-triazines; and (2) the substrate so protected e.g.,
the actinic screening layer plus the substrate.
[0029] The novel trisaryl-1,3,5-triazines of the present invention
may also employed to form light stabilizing compositions. Such
light stabilizing compositions may include a variety of other
components known in the art including other ultraviolet absorbers
and stabilizers, antioxidants and the like.
[0030] 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
[0031] The Amido or Carbamate Containing
Trisaryl-1,3,5-Triazines
[0032] As indicated above, the trisaryl-1,3,5-triazines in
accordance with the present invention are compounds of the general
formulas (I), (II) and (III).
[0033] As used herein, the term "amido containing
trisaryl-1,3,5-triazine" broadly refers to any compound of formulas
(I), (II) or (III) wherein at least one R group of a 4-position OR
group is an amido or amide group of the formula (V). As used
herein, the term "carbamate containing trisaryl-1,3,5-triazine"
broadly refers to any compound of formulas (I), (II) or (III)
wherein at least one R group of a 4-position OR group is a
carbamate group of the formula (VI).
[0034] 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.
[0035] 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 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 relevant
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 and, 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 displaced to create a valency on a
carbon or hetero atom in the hydrocarbyl chain or ring. As examples
of leaving groups may be mentioned halogen atoms such as chlorine,
bromine and iodine; 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. Preferred functionality
includes hydroxyl, --COOR.sup.11, --CR.sup.12.dbd.CH.sub.2,
--CO--CR.sup.12.dbd.CH.sub.2, OCO--CR.sup.12.dbd.CH.sub.2,
--OCO--NH--R.sup.9, Cl, 4
[0036] an isocyanate group, a blocked isocyanate group and
--NHR.sup.11
[0037] wherein R.sup.11 is selected from hydrogen and a hydrocarbyl
(preferably of up to 24 carbon atoms); and
[0038] R.sup.12 is selected from hydrogen and an alkyl of 1 to 4
carbon atoms (preferably hydrogen and methyl).
[0039] 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.).
[0040] 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.
[0041] The trisaryl-1,3,5-triazines in accordance with the present
invention also relate to latent stabilizing compounds against
actinic radiation of the general formulas (I), (II) and (III),
wherein at least one of the hydroxyl groups on an aryl ring ortho
to the point of attachment to the triazine 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 conversion of the O--X group to an OH
group, 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.
[0042] Latent stabilizing compounds comprising the amido or
carbamate containing trisaryl-1,3,5-triazines in accordance with
the present invention can be prepared from compounds of the general
formulas (I), (II) and (III) 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.
[0043] 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, or --CONHR.sup.h,
[0044] wherein 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;
[0045] 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;
[0046] 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;
[0047] 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
[0048] 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.
[0049] The reaction to give the latent stabilizing compounds of the
present invention of the general formulas (I), (II) and (III) 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 formulas (I), (II) and (III) 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, or
Cl--POR.sup.fR.sup.g. The reaction to give the latent stabilizing
compounds of the present invention of the general formulas (I),
(II) and (III) in which X is --CONHR.sup.h can be carried out, for
example, by reaction of the compounds of the general formulas (I),
(II) and (III) 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), (II) or (III).
[0050] Catalysts customarily used for acylation, sulfonylation,
phosphorylation, silylation or urethanation reactions may be used
in forming the latent stabilizing amido or carbamate containing
trisaryl-1,3,5-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.
[0051] 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.
[0052] In preferred embodiments, each X is hydrogen.
[0053] In preferred embodiments, those R groups which are not
either a group of the formula (V) or (VI) are independently
selected from hydrogen, a hydrocarbyl group of 1 to 24 carbon
atoms; and a functional hydrocarbyl group of 1 to 24 carbon atoms.
More preferably each such R group is independently selected from
hydrogen, an alkyl of 1 to 24 carbon atoms (which may optionally be
substituted by one or more hydroxyl, carboxyl, carboalkoxy (ester)
amide, epoxy and/or amino groups and/or contain one or more
carbonyl groups, oxygen atoms and/or nitrogen atoms in the chain);
an alkenyl of 2 to 24 carbon atoms (which may optionally be
substituted by hydroxyl, carboxyl, epoxy and/or amino group(s)
and/or contain carbonyl, oxygen and/or nitrogen in the chain), a
cycloalkyl of 5 to 24 carbon atoms (which may optionally be
substituted by hydroxyl, carboxyl and/or amino group(s) and/or
contain carbonyl, oxygen and/or nitrogen in the ring), and an
aralkyl of 7 to 24 carbon atoms (which may optionally be
substituted by hydroxyl, carboxyl and/or amino group(s) and/or
contain carbonyl, oxygen and/or nitrogen in the ring).
[0054] More preferably, each R group is independently selected from
hydrogen, an alkyl of 1 to 24 carbon atoms optionally containing an
oxygen atom in the chain, a hydroxyalkyl of 1 to 24 carbon atoms
group optionally containing an oxygen atom in the chain, a group of
the formula (V) and a group of the formula (VI), with the proviso
that at least one such R group is a group of the formula (V) or
(VI).
[0055] In preferred embodiments, each R.sup.1 is independently
selected from hydrogen, halogen, an acyl of 2 to 12 carbon atoms,
an acyloxy of 2 to 12 carbon atoms, a hydrocarbyl having from 1 to
24 carbon atoms and a functional hydrocarbyl having from 1 to 24
carbon atoms; more preferably from hydrogen, halogen, an alkyl of 1
to 24 carbon atoms, a functional alkyl of 1 to 24 carbon atoms, an
alkenyl of 2 to 24 carbon atoms, a cycloalkyl of 5 to 12 carbon
atoms; and especially hydrogen.
[0056] In preferred embodiments, each R.sup.2 is independently
selected from hydrogen, halogen, 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.2 is independently
selected from hydrogen, halogen, 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; and an acyloxy
group of 2 to 12 carbon atoms. Still more preferably, each R.sup.2
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, and an acyloxy of 2 to 12 carbon
atoms. Especially preferred is when each R.sup.2 is independently
selected from hydrogen and an alkyl of 1 to 4 carbon atoms and
particularly hydrogen and methyl.
[0057] In preferred embodiments, each R.sup.3 is independently
selected from hydrogen, halogen, a hydrocarbyl group of 1 to 24
carbon atoms, a functional hydrocarbyl group of 1 to 24 carbon
atoms and --OR. More preferably, each R.sup.3 is independently
selected from hydrogen, an alkyl of 1 to 24 carbon atoms (which may
optionally be substituted by hydroxyl, carboxyl and/or amino
group(s) and/or contain carbonyl, oxygen and/or nitrogen in the
chain); an alkenyl of 2 to 24 carbon atoms (which may optionally be
substituted by hydroxyl, carboxyl and/or amino group(s) and/or
contain carbonyl, oxygen and/or nitrogen in the chain); a
cycloalkyl of 5 to 12 carbon atoms (which may optionally be
substituted by hydroxyl, carboxyl and/or amino group(s) and/or
contain carbonyl, oxygen and/or nitrogen in the ring); and --OR.
Still more preferably, each R.sup.3 is independently selected from
hydrogen, an alkyl of 1 to 24 carbon atoms optionally containing an
oxygen atom in the chain, a hydroxyalkyl of 1 to 24 carbon atoms
group optionally containing an oxygen atom in the chain and --OR.
Especially preferred is when each R.sup.3 is independently selected
from hydrogen, an alkyl of 1 to 4 carbon atoms and --OR;
particularly hydrogen, methyl and --OR; and most particularly
hydrogen and methyl.
[0058] In preferred embodiments, each R.sup.4, R.sup.4 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.4, R.sup.4 and R.sup.4
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; and an acyloxy group of 2 to 12
carbon atoms. Still more preferably, each R.sup.4, R.sup.4 and
R.sup.4 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. Especially
preferred is when each R.sup.4, R.sup.4 and R.sup.4 is
independently selected from hydrogen and an alkyl of 1 to 4 carbon
atoms, and particularly hydrogen and methyl.
[0059] In preferred embodiments, each of R.sup.5 and R.sup.8 is
independently a hydrocarbylene group of 1 to 24 carbon atoms. More
preferably, each of R.sup.5 and R.sup.8 is independently selected
from an alkylene of 1 to 24 carbon atoms (which may optionally
contain carbonyl and/or oxygen in the chain); an alkenylene of 2 to
24 carbon atoms (which may optionally contain carbonyl and/or
oxygen in the chain) and a cycloalkylene of 5 to 12 carbon atoms
(which may optionally contain carbonyl and/or oxygen in the ring).
Still more preferably, each of R.sup.5 and R.sup.8 is independently
an alkylene of 1 to 24 carbon atoms optionally containing an oxygen
atom in the chain and especially an alkylene of 2 to 18 carbon
atoms optionally containing an oxygen in the chain.
[0060] In preferred embodiments, each of R.sup.6 and R.sup.7 is
independently selected from a hydrocarbyl group of 1 to 50 carbon
atoms and a functional hydrocarbyl group of 1 to 50 carbon atoms,
with at least one (and preferably only one) of R.sup.6 and R.sup.7
being such a functional hydrocarbyl group. As preferred examples of
functionality for the functional hydrocarbyl groups may be
mentioned hydroxyl, epoxy, --COOR.sup.11, --CR.sup.12.dbd.CH.sub.2,
--CO--CR.sup.12.dbd.CH.sub.2, --OCO--CR.sup.12.dbd.CH.sub.2,
--OCO--NH--R.sup.9, --NHR.sup.11 and a blocked isocyanate group.
More preferably, each of R.sup.6 and R.sup.7 is independently
selected from an alkyl group of 1 to 24 carbon atoms (which may
optionally contain carbonyl and/or one or more oxygen atoms in the
chain); an alkenyl group of 2 to 24 carbon atoms (which may
optionally contain carbonyl and/or one or more oxygen atoms in the
chain); a cycloalkyl group of 5 to 12 carbon atoms (which may
optionally contain carbonyl and/or one or more oxygen atoms in the
ring); and an aralkyl group of 7 to 24 carbon atoms, at least one
of which groups is substituted with a functional group as described
above. Still more preferably, each of R.sup.6 and R.sup.7 is
independently selected from an alkyl group of 1 to 24 carbon atoms
(which may optionally contain carbonyl and/or one or more oxygen
atoms in the chain), and an aralkyl group of 7 to 24 carbon atoms,
and at least one of which is substituted by a hydroxyl,
--CR.sup.12.dbd.CH.sub.2, --CO--CR.sup.12.dbd.CH.sub.2,
--OCO--CR.sup.12.dbd.CH.sub.2, --NHR.sup.11 and a blocked
isocyanate group.
[0061] In another preferred embodiment, R.sup.6 and R.sup.7 taken
together form a group selected from a functional hydrocarbylene
group having 3 to 24 carbon atoms, an unsaturated hydrocarbylene
group having 3 to 24 carbon atoms and an activated unsaturated
hydrocarbylene group having 3 to 24 carbon atoms. More preferable,
R.sup.8 and R.sup.7 taken together form a group selected from an
unsaturated hydrocarbylene group having 4 to 14 carbon atoms and an
activated unsaturated hydrocarbylene group having 4 to 14 carbon
atoms. As specific examples of R.sup.6 and R.sup.7 taken together,
in combination with the nitrogen, may be mentioned maleimide,
citraconimide, itaconimide, and the Diels-Alder adducts of
maleimide with dienes.
[0062] In preferred embodiments, R.sup.9 is selected from hydrogen,
a hydrocarbyl group of 1 to 50 carbon atoms and a functional
hydrocarbyl group of 1 to 50 carbon atoms. More preferably, R.sup.9
is selected from hydrogen, an alkyl of 1 to 24 carbon atoms (which
may optionally be substituted by a hydroxyl, and/or contain
carbonyl, oxygen and/or nitrogen in the chain); an alkenyl of 2 to
24 carbon atoms (which may optionally be substituted by a hydroxyl
and/or contain carbonyl, oxygen and/or nitrogen in the chain); a
cycloalkyl of 5 to 12 carbon atoms (which may optionally be
substituted by a hydroxyl and/or contain carbonyl, oxygen and/or
nitrogen in the ring); and an aralkyl of 7 to 24 carbon atoms
(which may optionally be substituted with a hydroxyl, --CR
.sup.12.dbd.CH.sub.2 or --CO--CR.sup.12.dbd.CH.sub.2). Still more
preferably, R.sup.9 is selected from hydrogen, an alkyl of 1 to 24
carbon atoms optionally containing an oxygen atom in the chain, and
an aralkyl of 7 to 24 carbon atoms, which may optionally be
substituted with a hydroxyl, --CR.sup.12.dbd.CH.sub.2 or
--CO--CR.sup.12.dbd.CH.sub.2. Especially preferred is when R.sup.9
is selected from hydrogen, an alkyl of 1 to 12 carbon atoms and an
aralkyl of 7 to 24 carbon atoms optionally substituted with
--CR.sup.12.dbd.CH.sub.2.
[0063] In preferred embodiments, R.sup.10 is hydrogen or an alkyl
of 1 to 24 carbon atoms, which may optionally contain oxygen in the
chain, and more preferably hydrogen.
[0064] 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.
[0065] 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.
[0066] 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.
[0067] Further preferred embodiments may include any combination of
the parameters mentioned above.
[0068] Particularly preferred embodiments of the
trisaryl-1,3,5-triazines of the general formula (I) are exemplified
by the following structures (VII), (VIII) and (IX): 5
[0069] Particularly preferred embodiments of the
trisaryl-1,3,5-triazines of the general formula (II) are
exemplified by the following structures (X), (XI) and (XII): 6
[0070] Particularly preferred embodiments of the
trisaryl-1,3,5-triazines of the general formula (III) are
exemplified by the following structures (XIII) and (XIV): 7
[0071] Preferred embodiments of groups of the general formula (V)
are those wherein
[0072] R.sup.5 is --(CHR.sup.14)n-;
[0073] R.sup.6 and R.sup.7 are each independently selected from the
group consisting of hydrogen, linear or branched alkyl of 1 to 24
carbon atoms, --(CH.sub.2).sub.nOH,
--(CH.sub.2)CH(OH)CH.sub.2OR.sup.15,
--(CH.sub.2)CH(OH)CH.sub.2R.sup.15 and 8
[0074] R.sup.14 and R.sup.15 are each independently selected from
hydrogen or linear or branched alkyl of 1 to 24 carbon atoms.
[0075] Other preferred embodiments of groups of the general formula
(V) are those wherein
[0076] R.sup.5 is --(CHR.sup.14)n-;
[0077] R.sup.6 is selected from the group consisting of hydrogen,
linear or branched alkyl of 1 to 24 carbon atoms,
[0078] --(CH.sub.2).sub.nOH, --(CH.sub.2)CH(OH)CH.sub.2OR.sup.15,
--(CH.sub.2)CH(OH)CH.sub.2R.sup.15 and 9
[0079] and
[0080] R.sup.7 is selected from the group consisting of a
polyoxyalkylene radical of the formula
--CH.sub.2CH(OH)CH.sub.2O(CH.sub.2(CH.sub.2).sub.mO).sub.p--D
[0081] in which D is hydrogen, 10
[0082] --CH.sub.2CH(OH)CH.sub.2OH or R.sup.16;
[0083] a polyoxyalkylene radical of the formula
--CO(CH.sub.2).sub.mO(CH.sub.2(CH.sub.2)O).sub.p--D.sub.2
[0084] in which D.sub.2 is --(CH.sub.2)mCOR.sup.17 or R.sup.16;
[0085] a polyoxyalkylene radical of the formula
--TOCO(CH.sub.2).sub.mO(CH.sub.2(CH.sub.2)O).sub.p--D.sub.3
[0086] in which D.sub.3 is --(CH.sub.2).sub.mCOR.sup.17 or
R.sup.16;
[0087] a polyoxyalkylene radical of the formula
--(CH.sub.2).sub.qCH(R.sup.18)COB.sub.1(C.sub.rH.sub.2rO).sub.p--C.sub.rH.-
sub.2rB.sub.1D.sub.4
[0088] in which D.sub.4 is hydrogen or R.sup.16;
[0089] a polyoxyalkylene radical of the formula
--COCH.sub.2CH.sub.2NH(C.sub.rH.sub.2rO).sub.p--C.sub.rH.sub.2rD.sub.5
[0090] in which D.sub.5 is --NH.sub.2,
--NH(CH.sub.2).sub.2COOR.sup.19 or or R.sup.16;
[0091] a polyoxyalkylene radical of the formula
--TOCOCH.sub.2CH.sub.2NH(C.sub.rH.sub.2rO).sub.p--C.sub.rH.sub.2rD.sub.5
[0092] in which D.sub.5 is --NH.sub.2,
--NH(CH.sub.2).sub.2COOR.sup.19 or or R.sup.16;
[0093] a polyoxyalkylene radical of the formula
--(C.sub.rH.sub.2rO).sub.p--C.sub.rH.sub.2rD.sub.6
[0094] in which D.sub.6 is --NHCOR.sup.20, --OH or hydrogen; or
[0095] a polyoxyalkylene radical of the formula
--CH(R.sup.21)CH.sub.2(OCH(R.sup.21)CH.sub.2).sub.p--D.sub.7
[0096] in which D.sub.7 is OR.sup.16, --NHCOR.sup.20 or
--OCH.sub.2CH.sub.2OR.sup.20.
[0097] Other preferred embodiments are dimeric
trisaryl-1,3,5-triazines of formula (XIV) wherein
[0098] R.sup.6 is selected from the group consisting of hydrogen,
linear or branched alkyl of 1 to 24 carbon atoms,
[0099] --(CH.sub.2).sub.nOH, --(CH.sub.2)CH(OH)CH.sub.2OR.sup.15,
--(CH.sub.2)CH(OH)CH.sub.2R.sup.15 and 11
[0100] and
[0101] R.sup.7 is a selected from the group consisting of alkylene
of 2 to 24 carbon atoms, alkenylene of 2 to 12 carbon atoms,
xylylene and alkylene of 3 to 24 atoms which is interrupted by one
or more oxygen atoms or substituted by --OH;
[0102] or a diradical of formula (XV) 12
[0103] wherein R.sup.22 is selected from alkylene of 2 to 10 carbon
atoms and alkylene of 4 to 50 carbon atoms which is interrupted by
one or more oxygen atoms or substituted by --OH;
[0104] or is a polyoxyalkylene bridge of the formula
--CH.sub.2CH(OH)CH.sub.2O(CH.sub.2(CH.sub.2).sub.mO).sub.pCH.sub.2CH(OH)CH-
.sub.2--;
[0105] or a polyoxyalkylene bridge of the formula
--CO(CH.sub.2).sub.mO(CH.sub.2(CH.sub.2).sub.mO).sub.p((CH.sub.2)mCO--;
[0106] or is a polyoxyalkylene bridge of the formula
--TOCO(CH.sub.2).sub.mO(CH.sub.2(CH.sub.2).sub.mO).sub.p(CH.sub.2).sub.mCO-
OT--;
[0107] or a polyoxyalkylene bridge of the formula
--(CH.sub.2).sub.qCHR.sup.23COB.sub.1(C.sub.rH.sub.2rO)p--C.sub.rH.sub.2rB-
.sub.1COCHR.sup.23(CH.sub.2).sub.q--;
[0108] or a polyoxyalkylene bridge of the formula
--COCH(R.sup.24)(CH.sub.2)NH(C.sub.rH.sub.2rO)p--C.sub.rH.sub.2rNHCH.sub.2-
CH(R.sup.24)CO--;
[0109] or a polyoxyalkylene bridge of the formula
--TOCO(CH.sub.2).sub.2NH(C.sub.rH.sub.2rO)p--C.sub.rH.sub.2rNH(CH.sub.2).s-
ub.2COOT--;
[0110] or a polyoxyalkylene bridge of the formula
--(C.sub.rH.sub.2rO)p--C.sub.rH.sub.2r--;
[0111] or a polyoxyalkylene bridge of the formula
--CH(CH.sub.3)CH.sub.2(OCH(CH.sub.3)CH.sub.2).sub.a(OCH.sub.2CH.sub.2).sub-
.b(OCH.sub.2CH(CH.sub.3).sub.c--;
[0112] in which a+c=2.5 and b=8.5 to 40.5, or a+c=2 to 33 and
b=0.
[0113] Wherein R.sup.16 is alkyl of 1 to 18 carbon atoms;
[0114] R.sup.17 is halogen or R.sup.19;
[0115] R.sup.18 is hydrogen or alkyl of 1 to 18 carbon atoms;
[0116] R.sup.19 is hydrogen, alkyl of 1 to 18 carbon atoms, alkenyl
of 3 to 18 carbon atoms, aryl of 6 to 18 carbon atoms or aralkyl of
7 to 18 carbon atoms;
[0117] R.sup.20 is hydrogen, alkyl of 1 to 12 carbon atoms or aryl
of 6 to 12 carbon atoms;
[0118] R.sup.21 is hydrogen or alkyl of 1 to 4 carbon atoms;
[0119] R.sup.23 is hydrogen or alkyl of 1 to 16 carbon atoms;
[0120] R.sup.24 is hydrogen, alkyl of 1 to 4 carbon atoms or
CN;
[0121] m is a number from 1 to 4;
[0122] p is a number from 2 to 60;
[0123] q is zero or a number from 1 to 16;
[0124] r is 2 to 6;
[0125] B.sub.1 is a bridging group selected from --O--, --NH-- or
--NR.sup.18--; and
[0126] T is unsubstituted or substituted alkylene of 2 to 20 carbon
atoms.
[0127] Particularly preferred embodiments of groups of the general
formula (V) include the following: 13
[0128] wherein n is 1-24 (preferably 1-18, and especially 1-8), n1
is 0-23 (preferably 0 to 17), n2 is 1-24 (preferably 1-10) and n3
is 1-24 (preferably 1 to 8).
[0129] Particularly preferred embodiments of groups of the general
formula (VI) include the following: 14
[0130] wherein n and n1 are as defined above.
[0131] Methods of Preparation
[0132] The amido or carbamate containing trisaryl-1,3,5-triazines
of the present invention can be prepared by a multistep process in
which a 4-hydroxyl precursor is appropriately functionalized, by
analogy to the procedures described in a number of the previously
incorporated references such as U.S. Pat. No. 3,244,708 and
EP-A-0434608.
[0133] In a preferred method for preparing the amido functional
triazine compounds, a precursor compound corresponding to the
formulas (I), (II) or (III), except where at least one (and
preferably all) R groups are hydrogen, is reacted in a first step
with a haloacetate (e.g., ethyl chloroacetate) to prepare an
acetate functional intermediate, which is subsequently reacted with
an appropriate secondary amine to prepared the desired amido
functional end product.
[0134] The reaction of the precursor compound with the haloacetate
may be conducted under appropriate acylating conditions known to
those of ordinary skill in the art. Preferably, the reaction is
carried out in the presence of an inert solvent, such as
acetonitrile, acetone, methyl ethyl ketone, methyl isobutyl ketone,
dimethylformamide, dioxane, tetrahydrofuran, and aromatic
hydrocarbons such as toluene and xylene. The reaction is also
preferably carried out in the presence of a catalyst such as an
alkali metal iodide like sodium or potassium iodide. A base is also
preferably present, such as an alkali metal hydroxide (sodium or
potassium hydroxide), alkali metal carbonate or bicarbonate, or
tertiary amine (triethylamine). Reaction temperatures may vary
widely depending on the starting components; however, temperatures
of 100.degree. C. or less are preferred to avoid undesired reaction
of the 2-hydroxyl group.
[0135] The reaction of the resulting acetate functional
intermediate with the secondary amine is preferably carried out
under appropriate transesterification/amidation conditions known to
those of ordinary skill in the art. Preferably, the reaction is
carried out in the presence of a solvent as set forth above, and
further in the presence of a transesterification/amidation
catalyst. Examples of suitable transesterification/amidation
catalysts include the titanates such as tetra-i-propyltitanate
(TYZOR.RTM. TPT) (titanium (IV) isoproxide) tetrabutyltitanate
(TYZOR.RTM. TBT) (titanium (IV) butoxide), alkali and alkaline
earth salts of .beta.-ketoesters and .beta.-diketones such as
calcium and magnesium salts of acetoacetic acid, alkoxides and
oxides of alkali and alkaline earth metals such as sodium,
potassium, calcium and magnesium, tertiary amines such as
4-dimethylaminopyridine), and strong protonic acids such as
H.sub.2SO.sub.4, HCl and p-toluenesulfonic acid, which may
optionally be supported on inert supports, and transition metal
salts such as zinc, nickel, copper or cobalt acetate. The reaction
is preferably carried out under reflux conditions, with the removal
of volatile alcohol by-products.
[0136] In another preferred process for preparing the amido
functional compounds in accordance with the present invention, the
precursor compound mentioned above (wherein the R groups are H) can
be reacted in a first step with a hydroxyalkyl halide (under
conditions well-known to those of ordinary skill in the art) to
prepare a hydroxyalkyl functional intermediate, which is
subsequently reacted with the haloacetate and secondary amine as
described above.
[0137] Another preferred process is a variation on the
above-described processes, in which the precursor compound
mentioned above is reacted with a pre-react of the above mentioned
functionalizing reactants (varying the order of reaction) for
example, preparing a pre-react of an haloacetate and secondary
amine, then reacting this pre-react further with the precursor
compound.
[0138] The carbamate functional compounds in accordance with the
present invention are also preferably prepared by reacting the
aforementioned hydroxyalkyl functional intermediate with an
isocyanate functional compound such as
1-(2-isocyanatoisopropyl)-3-isopropenylbenzene ("m-TMI"), or a
blocked isocyanate functional compound such as methyl carbamate
(transcarbamylation). This reaction is preferably carried out in an
inert solvent such as xylene, and further in the presence of a
well-known urethane base or organometallic catalyst.
[0139] The resulting amido and carbamate functional compounds may
be further functionalized if and as desired. For example, in the
preparation of the amide functional triazine compound, the use of
an hydroxyalkyl amine as the secondary amine results in a
hydroxyalkyl functional amide. The hydroxyl group may be further
reacted with, for example, an unsaturated acid such as
(meth)acrylic acid, a halo compound such as allyl chloride, an
epoxy functional compound such as ethylene or propylene oxide,
and/or an isocyanate functional compound such a m-TMI, to impart
other or additional functionality to the molecule.
[0140] Specific preferred preparative procedures are detailed in
the examples annexed hereto.
[0141] Uses of the Trisaryl-1,3,5-Triazines
[0142] As indicated earlier, the novel amido and carbamate
containing trisaryl-1,3,5-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
amido or carbamate containing trisaryl-1,3,5-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.
[0143] In one embodiment of the present invention, the amido or
carbamate containing trisaryl-1,3,5-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 such materials, especially organic
polymers, either chemically or physically. Examples of polymers
which can be stabilized include, but are not limited to:
[0144] 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 norbomene; 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).
[0145] 2. Copolymers of one or more monoolefins and/or diolefins
with carbon monoxide and/or with other vinyl monomers, including
limited 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 allyglycidyl ether and derivatives thereof.
[0146] 3. Hydrocarbon resins (such as C.sub.5-C.sub.9) including
hydrogenated modifications thereof and mixtures of polyalkylenes
and starch.
[0147] 4. Homo- and copolymers of styrenes such as styrene,
p-methylstyrene and amethyistyrene.
[0148] 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.
[0149] 6. Graft copolymers of styrenes on polybutadienes,
polybutadiene/styrene copolymers and polybutadiene/acrylonitrile
copolymers; styrene (or a-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.
[0150] 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.
[0151] 8. Homo- and copolymers derived from
.alpha.,.beta.-unsaturated acids and derivatives thereof such as
acrylic acid, methacrylic acid, acrylates, methacrylates,
acrylamides and acrylonitriles.
[0152] 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.
[0153] 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.
[0154] 11. Homo- and copolymers of cyclic ethers such as alkylene
glycols and alkylene oxides, as well as copolymers with bisglycidyl
ethers.
[0155] 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.
[0156] 13. Polyphenylene oxides and sulfides.
[0157] 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.
[0158] 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).
[0159] 16. Polyureas, polyimides, polyamide-imides,
polyetherimides, polyesterimides, polyhydantoins and
polybenzimidazoles.
[0160] 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 hydroxylterminated ethers; and also polyesters modified with
polycarbonate or MBS.
[0161] 18. Polycarbonates and polyester carbonates.
[0162] 19. Polysulfones, polyether sulfones and polyether
ketones.
[0163] 20. Crosslinked polymers derived from aldehydes condensation
resins such as phenol/formaldehyde resins, urea/formaldehyde resins
and melamine/formaldehyde resins.
[0164] 21. Drying and non-drying alkyd resins.
[0165] 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.
[0166] 23. Crosslinkable acrylic resins derived from substituted
acrylates such as epoxy acrylates, hydroxy acrylates, isocyanato
acrylates, urethane acrylates or polyester acrylates.
[0167] 24. Alkyd resins, polyester resins and acrylate resins
crosslinked with melamine resins, urea resins, isocyanates,
isocyanurates, carbamates or epoxy resins.
[0168] 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
customary hardeners such as anhydrides or amines.
[0169] 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.
[0170] 27. Polysiloxanes.
[0171] 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.
[0172] 29. Mixtures or blends of any of the above, such as PP/EPDM,
polyarnide/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, PA/HDPE, PP/HDPE, PP/LDPE,
LDPE/HDPE, LDPE/EVA, LDPE/EAA, PA/PP, PA/PPO, PBT/PC/ABS,
PBT/PET/PC and the like.
[0173] 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.
[0174] 31. Radiation curable compositions containing ethylenically
unsaturated monomers or oligomers and a polyunsaturated aliphatic
oligomer.
[0175] 32. Epoxymelamine resins such as light-stable epoxy resins
cross-linked by an epoxy functional coetherified high solids
melamine resin.
[0176] Other materials which can be stabilized include, for
example:
[0177] 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.
[0178] 34. Aqueous emulsions of natural or synthetic rubber such as
natural latex or lattices of carboxylated styrene/butadiene
copolymers.
[0179] 35. Organic dyes such as azo dyes (diazo, triazo and
polyazo), anthraquinones, benzodifu ranones, 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.
[0180] 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.
[0181] 37. Cellulose-based paper formulations for use, e.g., in
newsprint, cardboard, posters, packaging, labels, stationery, book
and magazine paper, bond typing paper, multipurpose and office
paper, computer paper, xerographic paper, laser and ink-jet printer
paper, offset paper, currency paper, etc.
[0182] 38. Photographic film paper.
[0183] 39. Ink.
[0184] As mentioned above, one particular advantage of the amido or
carbamate containing trisaryl-1,3,5-triazines of the present
invention is that they can be chemically bound 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
covalent) 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.
[0185] Incorporation of the trisaryl-1,3,5-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 previously incorporated U.S. Pat. Nos. 3,423,360 and
5,189,084.
[0186] Bonding of the trisaryl-1,3,5-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.
[0187] In addition, bonding of the presently claimed amido or
carbamate containing trisaryl-1,3,5-triazine compounds of the
present invention of the formulas (I), (II), or (III) 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 formulas
(I), (II), or (III) 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.
[0188] In addition, compounds of the formulas (I), (II), or (III)
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. Analagous
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.
[0189] Alternately, the trisaryl-1,3,5-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 analagous
to those well known to those of ordinary skill in the art.
[0190] Grafting is yet another way of bonding of the presently
claimed amido or carbamate containing trisaryl-1,3,5-triazine
compounds of the formulas (I), (II), or (III) 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 amido or carbamate containing
trisaryl-1,3,5-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.
[0191] The amido or carbamate containing trisaryl-1,3,5-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 trisaryl-1,3,5-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.
[0192] 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.
[0193] Incorporation into the thermoplastic polymers can be carried
out by addition of the novel amido or carbamate containing triazine
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.
[0194] 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.
[0195] 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.
[0196] 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.
[0197] Depending upon their ultimate end use, the amido or
carbamate containing trisaryl-1,3,5-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:
[0198] a. Antioxidants
[0199] (i) Alkylated monophenols such as
2,6-di-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-(a-methylcyclohexyl)-4,6-dimethylphen- ol;
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.
[0200] (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.
[0201] (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.
[0202] (iv) Tocopherols such as .alpha.-tocopherol,
.beta.-tocopherol, y-tocopherol, .delta.-tocopherol and mixtures
thereof (vitamin E).
[0203] (v) Hydroxylated thiodipbenyl 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.
[0204] vi) Alkylidenebisphenols such as
2,2'-methylenebis(6-tert-butyl-4-m- ethylphenol);
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'-methylenebis(4,6-di-tert-butylphenol);
2,2'-ethylidenebis(6-tert-but- yl-4-isobutylphenol);
2,2'-methylenebis[6-(.alpha.-methylbenzyl)-4-nonylph- enol];
2,2'-methylenebis[6-(.alpha.,.alpha.-dimethylbenzyl)-4-nonylphenol]-
; 4,4'-methylenebis(2,6-di-tert-butylphenol);
4,4'-methylenebis(6-tert-but- yl-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.
[0205] (vii) O--, N-- and S-benzyl compounds such as
3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether;
octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate;
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- .
[0206] (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.
[0207] (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.
[0208] (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.
[0209] (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.
[0210] (xii) Acylaminophenols such as 4-hydroxylauranilide;
4-hydroxystearanilide; and octyl
N(3,5-di-tert-butyl-4-hydroxyphenyl)carb- amate.
[0211] (xiii) Esters of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propioni- c 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.
[0212] (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.
[0213] (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.
[0214] (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.
[0215] (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.
[0216] (xviii) Ascorbic acid (Vitamin C).
[0217] (xix) Aminic antioxidants such as
N,N'-diisopropyl-p-phenylenediami- ne;
N,N'-di-secbutyl-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-phenylenediaamine;
N-cyclohexyl-N'-phenyl-- pphenylenediamine;
4-(p-toluenesulfonamoyl)diphenylamine;
N,N'-dimethyl-N,N'-disec-butyl-p-phenylenediamine; diphenylamine;
N-allyldiphenylamine; 4-isopropoxydiphenylamine;
N-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 tertbutyldiphenylamines;
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; Nallylphenothiazine;
N,N,N',N'-tetraphenyl-1,4-- diaminobut-2-ene;
N,N-bis(2,2,6,6-tetramethylpiperid-4-yl)hexamethylenedia- mine;
bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate;
2,2,6,6-tetramethylpiperidin-4-one; and
2,2,6,6-tetramethylpiperidin-4-UV- -absorbers and light
stabilizers
[0218] (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'--
hydroxyphenyl)-benzotriazole; 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-ethylhexyloxycarbonylethyl)phenyl-2'-hydroxyphe-
nyl)benzotriazole, 2-(3'-dodecyl-2'-
hydroxy-5'-methylphenyl)benzotriazole ;
2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzot-
riazole;
2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-yl-
phenol]; a mixture of the transesterification product of
2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]benzotriazo-
le with polyethylene glycol 300;
[R--CH.sub.2CH.sub.2--CO(CH.sub.2CH.sub.2- ].sub.2--where
R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl;
2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(.alpha.,.alpha.'-dimethyl-
benzyl)phenyl]benzotriazole and
2-[2'-hydroxy-3'-(.alpha.,.alpha.'-dimethy-
lbenzyl)-5'-(1,1,3,3-tetramethylbutyl)phenyl]benzotriazole.
[0219] (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.
[0220] (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.
[0221] (iv) Acrylates and benzylide malonates such as ethyl
.alpha.-cyano-.beta.,.beta.-dephenylcrylate; 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 and
propanedioic acid,[(4-methoxyphenyl)met- hylene]-, dimethyl
ester.
[0222] (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-hydroxypyr- azole,
with or without additional ligands.
[0223] (vi) Sterically hindered amines as well as the N derivatives
thereof (e.g., N-alkyl, N-hydroxy, N-alkoxy and N-acyl), such as
monomeric HALS, including 4-benzoyl-2,2,6,6-tetramethylpiperidine;
4-stearyloxy-2,2,6,6-tetramethylpiperidine; a mixture of
4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine;
1-octyloxy-2,2,6,6-tetram- ethylpiperidin-4-yl methacrylate;
2-(2-hydroxyethylamino)-4,6-bis(4-n-buty-
lamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine;
bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate;
bis(2,2,6,6-tetramethylpi- peridin-4-yl)succinate;
bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate;
bis(1,2,2,6,6-pentamethylpiperidin-4-yl)succinate;
bis(l-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)succinate;
3-n-dodecyl-7,7,9,9-tetramethyl-
1,3,8-triazaspiro[4.5]decan-2,4-dione;
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione;
bis(1,2,2,6,6-pentamethylpiperidin-4-yl)
2-n-butyl-2-3,5-di-tert-butyl-4-- hydroxybenzyl)malonate;
3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyr-
rolidin-2,5-dione; 3-dodecyl-
1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrro- lidin-2,5-dione;
3-dodecyl- 1-(1-ethanoyl-2,2,6,6-tetranethylpiperidin-4-y-
l)pyrrolidin-2,5-dione; 2-undecyl-7,7,9,9-tetramethyl-
1-oxa-3,8-diaza-4-oxospiro[4.5]decane;
7-oxa-3,20-diazadispiro[5.1.11.2]h- eneicosane-20-propanoic acid,
2,2,4,4-tetramethyl-21-oxo-, dodecyl ester;
2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane;
b-alanine, N-(2,2,6,6-tetramethyl-4-piperidinyl)-, mixture of
dodecyl and tetradecyl esters;
N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,3-benzen-
edicarboxamide;
tris(2,2,6,6-tetramethylpiperidin-4-yl)nitrilotriacetate;
tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylat-
e;
N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylened-
iamine; Oligomeric/polymeric HALS such as the condensate of
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and
dimethyl succinate; the condensate of
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hyd- roxypiperidine and
succinic acid; the condensate of
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and
2,2-diethylmalonic acid; the condensate of
N,N'-bis(2,2,6,6-tetramethylpi- peridin-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)he-
xamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine;
the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenedia- mine
and 4-cyclohexylamino-2,6-dichloro-l triazine; the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine,
2,4-dichloro- the condensate of
2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-t-
etramethylpiperidyl)-1,3,5-triazine and
1,2-bis(3-aminopropylamino)ethane; the condensate of
2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpi-
peridyl)-1,3,5-triazine and 1,2-bis-(3-aminopropylamino)ethane;
poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane;
the reaction product of
7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4--
oxospiro[4.5]decane and epichlorohydrin; reaction product of maleic
acid anhydride-a-olefin-copolymer with
2,2,6,6-tetramethyl-4-aminopiperidine or
1,2,2,6,6-pentamethyl-4-aminopiperidine; and other HALS including
photobondable HALS such as propanedioic acid,
{(4-methoxyphenyl)methylene- }-,
bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester; propanedioic acid,
[(4-methoxyphenyl)methylene]-,
bis(1-acetyl-2,2,6,6-pentamethyl-4-piperid- inyl) ester, and
similar materials disclosed in GB-A-2269819;
oxo-piperanzinyl-triazines or so-called PIP-T HALS, e.g.,
1,1'-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone);
1,1',1"-[1,3,5-triazine-2,4,6-triyltris[(cyclohexylimino)-2,1-ethanediyl]-
]tris[3,3,5,5-tetramethylpiperazinone];
1,1',1"-[1,3,5-triazine-2,4,6-triy-
ltris[(cyclohexylimino)-2,1-ethanediyl]]tris[3,3,4,5,5-pentamethylpiperazi-
none] and similar materials disclosed in U.S. Pat. No.
5,071,981.
[0224] See also generally J. Pospisil and P. P. Klemchuk, Oxidation
Inhibition in Organic Materials, Vol., II (1990), pp. 58-60, U.S.
Pat. Nos. 4,619,956, 5,106,891, EP-A-0309400, EP-A-0309401,
EP-A-0309402 and EP-A-0434608.
[0225] bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate;
bis(2,2,6,6-tetramethylpiperidin-4-yl) succinate; bis(1,2,2,6,6-
pentamethylpiperidin-4-yl)sebacate;
bis(1-octyloxy-2,2,6,6-tetramethylpip- eridin-4-yl)sebacate;
bis(1,2,2,6,6-pentarnethylpiperidin-4-yl) n-butyl
3,5-di-tert-butyl-4- hydroxybenzylmalonate; the condensate of
1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and
succinic acid; the condensate of N,N'-bis(2,2,6,6-
tetramethylpiperidin-4-yl)hexam- nethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-triazine;
tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate;
tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylat-
e; 1,1'-(1,2- ethanediyl)bis(3,3,5,5-tetramethylpiperazinone);
4-benzoyl-2,2,6,6- tetramethylpiperidine;
4-stearyloxy-2,2,6,6-tetramethy- lpiperidine; bis(1,2,2,6,6-
pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3-
,5-di-tert-butylbenzyl) malonate;
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-tria-
zaspiro[4.5]decan-2,4-dione;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)s- ebacate;
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate; the
condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenedia- mine
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-tetramethylpip- eridine; the condensate of
N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexa- methylenediamine
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.
[136504-96-61);
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 U5461 9956, U.S. Pat. No. 5,106,891, GB-A-2269819,
EPA-0309400, EP-A-0309401, EP-A-0309402 and EP-A-0434608, which (to
the extent not already done so) are incorporated herein by
reference as if fully set forth.
[0226] (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 pethoxy
disubstituted oxanilides.
[0227] (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-bis(4-methylphenyl)-1,3,5-triazine;
2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazi-
ne;
2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-tr-
iazine;
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-octyloxypropyl-
oxy)phenyl]-4,6bis(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;
and 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-
triazine.
[0228] (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.
[0229] (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)methylp-
hosphite; and bis(2,4-di-tert-
butyl-6-methylphenyl)ethylphosphite.
[0230] (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.
[0231] (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-hexadecylalpha-heptadecyl
nitrone; N-octadecyl-alpha-pentadecy- l nitrone;
N-heptadecyl-alphaheptadecyl nitrone; N-octadecyl-alpha-hexadec- yl
nitrone; and nitrones derived from N,N-dialkylhydroxylamines
prepared from hydrogenated tallow fatty amines.
[0232] (g) Thiosynergists such as dilauryl thiodipropionate and
distearyl thiodipropionate.
[0233] (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.
[0234] (i) Polyamide stabilizers such as copper salts in
combination with iodides and/or phosphorus compounds and salts of
divalent manganese.
[0235] (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.
[0236] (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 ("ionomers").
[0237] (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.
[0238] (m) Other additives such as plasticizers, lubricants,
emulsifiers, pigments, rheological additives, catalysts, levelling
assistants, optical brighteners, flameproofing agents, antistatic
agents and blowing agents.
[0239] (n) Benzofuranones and indolinones such as those disclosed
in U.S. Pat. Nos. 4,325,863, 4,338,244, 5,175,312, 5,216,052,
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)-phenyllbenzofuran-2-one;
3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxyphenyl)benzofuran-2-one];
5,7-di-tert-butyl-3-)4-eethoxyphenyl)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.
[0240] The novel amido or carbamate containing
trisaryl-1,3,5-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 analagous 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 presently
claimed amido or carbamate containing trisaryl-1,3,5-triazine
compounds of the present invention of the formulas (I), (II), or
(III).
[0241] 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.
[0242] In another embodiment of the present invention, the novel
mixtures comprising compounds of the formulas (I), (II), or (III)
can be used as stabilizers for coatings, for example for paints
such as disclosed in numerous of the previously incorporated
references (see, e.g., U54619956, U54740542, U54826978, U54962142,
U55106891, USS 1984,98, U.S. Pat. No. 5,298,067, U55322868, U.S.
Pat. Nos. 5,354,794, 5,369,140, U55420204, U.S. Pat. No. 5,461,151,
U55476937, 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.
[0243] 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 amido or carbamate containing
trisaryl-1,3,5-triazines of the present invention.
[0244] Multilayer systems are possible here as well (such as
electrocoat/basecoatlclearcoat 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.
[0245] 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.
[0246] 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 incude acrylics, polyesters, polyurethanes
and PVC plastisols. Examples of curable binders include functional
alkyd, acrylic, polyester, phenolic, melamine, epoxy and
polyurethane resins and mixtures thereof.
[0247] 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 which is
incorporated herein by reference. Preferred binders include those
which comprise a functional acrylate resin and a crosslinking
agent.
[0248] 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:
[0249] 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;
[0250] 2. two-component polyurethane paints based on
hydroxyl-containing acrylate, polyester or polyether resins and
aliphatic or aromatic isocyanates, isocyanurates or
polyisocyanates;
[0251] 3. one-component polyurethane paints based on blocked
isocyanates, isocyanurates or polyisocyanates which are deblocked
during baking;
[0252] 4. two-component paints based on (poly)ketimines and
aliphatic or aromatic isocyanates, isocyanurates or
polyisocyanates;
[0253] 5. two-component paints based on (poly)ketimines and an
unsaturated acrylate resin or a polyacetoacetate resin or a
methacrylamidoglycolate methyl ester;
[0254] 6. two-component paints based on carboxyl- or
amino-containing polyacrylates and polyepoxides;
[0255] 7. two-component paints based on acrylate resins containing
anhydride groups and on a polyhydroxy or polyamino component;
[0256] 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;
[0257] 9. two-component paints based on unsaturated polyacrylates
and polymalonates;
[0258] 10. thermoplastic polyacrylate paints based on thermoplastic
acrylate resins or externally crosslinking acrylate resins in
combination with etherified melamine resins;
[0259] 11. paint systems based on siloxane-modified or
fluorine-modified acrylate resins.
[0260] In addition to the binder and novel amido or carbamate
containing trisaryl-1,3,5-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 amido or carbamate triazine is 4:1 to 1:4. More
preferably, the weight ratio of benzotriazole to amido or carbamate
triazine is 2:1 to 1:2.
[0261] 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 ainido or carbamate containing
trisaryl-1,3,5-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.
[0262] 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: 15
[0263] in which G is, for example, hydrogen, hydroxyl, alkyl (such
as methyl), alkoxy (such as ethoxy) or acyl.
[0264] More preferably the stabilizer is a
2,2,6,6-tetraalkylpiperidine derivative containing at least one
group of the formula: 16
[0265] in which G is, for example, hydrogen, hydroxyl, alkyl (such
as methyl), alkoxy (such as methoxy) or acyl.
[0266] 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, 5,461,151 and
EP-A-0434608 which (to the extent not already done so) 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):
[0267] bis(2,2,6,6-tetramethylpiperid-4-yl) succinate;
bis(2,2,6,6-tetramethylpiperid-4-yl) sebacate;
[0268] bis(1,2,2,6,6-pentamethylpiperid-4-yl) sebacate;
bis(1-octyloxy-2,2,6,6-tetramethylpiperid-4-yl) sebacate;
di(1,2,2,6,6-pentamethylpiperid-4-yl)
2-n-butyl-2-(3,5-di-tert-butyl-4-hy- droxybenzyl)malonate;
1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl methacrylate;
2-(2-hydroxyethylamino)-4,6-bis(4-n-butylamino-1,2,2,6,6-pe-
ntamethylpiperidyl)-1,3,5-triazine;
[0269] tetra(2,2,6,6-tetramethylpiperid-4-yl)
butane-1,2,3,4-tetracarboxyl- ate;
[0270] tetra(1,2,2,6,6-pentamethylpiperid-4-yl)
butane-1,2,3,4-tetracarbox- ylate;
2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21
-oxo-dispiro[5.1.11.2]henei- cosane; 3-dodecyl-
1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dio- ne;
3-dodecyl-1-(1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-
-dione, propanedioic acid, [(4-methoxyphenyl)methylene]-,
bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester; propanedioic acid,
[(4-methoxyphenyl)methylene]-,
bis(l-acetyl-2,2,6,6-pentamethyl-4-piperid- inyl) ester.
[0271] Commercially available examples of these and other
tetraalkylpipieridine derviatives include SANDUVOR.RTM. 3050, 3051,
3052, 3055, 3056, 3058, PR-31 and PR-32 (Clariant Corp.);
TINUVIN.RTM. 079L, 123,144, 292, 440L and 622LD (Ciba Specialty
Chemicals); CHIMASSORB.RTM. 119 and 944 (Ciba Specialty Chemicals);
and CYASORB.RTM. UV-3346, UV 3529, UV-3853, LV-500 and UV-516
(Cytec Industries, Inc.)
6-(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine, and
di-n-butylamine. Apart from the binder, the amido or carbamate
containing trisaryl-1,3,5-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).
[0272] Possible drying catalysts or curing catalysts are, for
example, organometallic compounds, amines, amino-containing resins
and/or phosphines.
[0273] 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, Ti 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, ohydroxyacetophenone or ethyl
trifluoroacetylacetate and the alkoxides of these metals. Examples
of organotin compounds are dibutyltin oxide, dibutyltin dilaurate
or dibutyltin dioctoate.
[0274] 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.
[0275] The curing catalyst used can also be a phosphine, for
example triphenylphosphine.
[0276] Another type of curing catalyst is a peroxide which can be
used, for example, to cure a gel coating for a fiberglass
article.
[0277] 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.
[0278] The novel coating compositions according to the invention
can be applied to any desired substrates, for example to metal,
wood, plastic, fibergalss 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.
[0279] 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.
[0280] Depending on the binder system, the coatings can be cured at
room temperature or by heating. Thermosettig coatings are
preferably cured at 50-150.degree. C. and, in the case of powder
coatings, even at higher temperatures.
[0281] 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.
[0282] 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 (III) 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.
[0283] 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 an amido or
carbamate substituted trisaryl-1,3,5-triazine, and to the use of
mixtures comprising an amido or carbamate substituted
trisaryl-1,3,5-triazine compound in coating compositions as
stabilizers against damage by light, oxygen and/or heat.
[0284] 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).
[0285] The pigments can be inorganic, organic or metallic pigments.
The novel coating compositions preferably contain no pigments and
are used as a clearcoat.
[0286] 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.
[0287] The amido or carbamate triazines of this invention may be
applied topically by polishing a surface with a composition
comprising the amido or carbamate 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.
[0288] Preference is also given to the use of the novel amido or
carbamate substituted trisaryl-1,3,5-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 amido or carbamate substituted
trisaryl-1,3,5-triazine compound.
[0289] 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.
[0290] 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.
[0291] In particular, it is possible successfully to stabilize
photographic materials similar to those described in U.S. Pat. No.
4,518,686.
[0292] 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 an amido or carbamate substituted
trisaryl-1,3,5-triazine compound.
[0293] Preference is additionally given to photographic materials
which have a layer comprising a compound of the formula (I), (II)
or (III) above the uppermost silver-halide emulsion layer and/or
between the green- and red-sensitive silver-halide emulsion
layers.
[0294] 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 (III)
must be present at least in one layer.
[0295] The novel material preferably has gelatin interlayers
between the silver-halide emulsion layers.
[0296] Preference is given to photographic materials in which the
silver halide in the bluesensitive, green-sensitive and/or
red-sensitive layer is silver chloride bromide comprising at least
90 mol % of silver chloride.
[0297] The compounds of the formula (I), (II) or (III) 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 and also alkylamides
and phenols.
[0298] 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.
[0299] The amido or carbamate substituted trisaryl-1,3,5-triazine
compounds of the formula (I), (II) or (III) 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 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 polyainide
fibers. A furrther 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.
[0300] To this end, one or a number of different compounds of the
formula (I), (II) or (III) 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.
[0301] The amido or carbamate substituted trisaryl-1,3,5-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.
[0302] The textile fiber materials finished with the novel
compounds of the formula (I), (II) or (III) 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 amido or
carbamate substituted trisaryl-1,3,5-triazine compound has,
relative to untreated fabric, a greatly increased sun protection
factor (SPF).
[0303] 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 (III) are permeable to UV radiation. The determination of
the sun protection factor of textile fiber materials is explained,
for example, in W094/04515 or in J. Soc. Cosmet. Chem. 40,
127-133(1989) and can be carried out analogously thereto.
[0304] Yet another use of the UV absorbers according to the
invention is in the stabilization of intra-ocular and contact
lenses.
[0305] The UV absorbers according to the invention are suitable,
furthermore, as photoprotective agents in cosmetic preparations.
The invention additionally relates, therefore, to a cosmetic
preparation comprising at least one amido or carbamate substituted
trisaryl-1,3,5-triazine compound and cosmetically acceptable
carriers or auxiliaries.
[0306] 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 an amido or carbamate substituted
trisaryl-1,3,5-triazine UV absorber and a cosmetically acceptable
auxiliary.
[0307] 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.
[0308] 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.
[0309] 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 mentioned can comprise any oil which is suitable for
cosmetic formulations, for example 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.
[0310] For the cosmetic formulations according to the invention it
is possible to use any conventionally employed emulsifier, for
example one or more ethoxylated esters of naturally occurring
derivatives, for example 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.
[0311] 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.
[0312] 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.
[0313] 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
[0314] Preparation of Compound A (Intermediate)
[0315]
2-(2-hydroxy-4-ethoxycarbonylmethoxyphenyl)-4,6-bis(2,4-dimethylphe-
nyl)-1,3,5-triazine (Compound "A") was synthesized using the
following reaction scheme: 17
[0316] The following were added, from first to last, to a 2 neck
round bottom flask equipped with a magnetic stirring bar, a reflux
condenser, an argon inlet and a rubber septum:
[0317] 8.0 g of
2,4-bis(2,4-dimethylphenyl)-6-(2,4-dihydroxyphenyl)-1,3,5--
triazine,
[0318] 6.92 g of anhydrous K.sub.2CO.sub.3,
[0319] 50 ml of acetone,
[0320] 2.7 g ethyl chloroacetate and
[0321] 332 mg potassium iodide.
[0322] The reaction mixture was stirred for 2 h as its temperature
was gradually increased to 40.degree. C. Then the temperature was
rapidly increased to 60.degree. C. and the mixture was further
stirred for 7 h. Thin layer chromatography (hereafter "tlc")
analysis after the 7 h stirring indicated the presence of Compound
A and no starting triazine material. The reaction mixture was
cooled to room temperature, diluted with 50 ml of methylene
chloride, then filtered through Celite. The filter cake was washed
with methylene chloride. The combined filtrates were concentrated
at reduced pressure to yield 10.4 g of crude Compound A which was
crystallized from a methylene chloride-methanol mixed solvent to
give 8.7 g of a substantially pure product, as determined by
.sup.1H NMR, .sup.13C NMR and mass spectroscopy.
[0323] Preparation of Compound B (Comparative)
[0324]
4-[4,6-Bis(2'4'-dimethylphenyl)-1,3,5-triazin-2-yl]-3-hydroxyphenox-
yacetic acid, N-(2-hydroxyethyl)amide (Compound "B"); also known as
2-[2-hydroxy-4-(N-2-hydroxyethyl)-methanamidooxy)phenyl]-4,6-bis(2,4-dime-
thylphenyl)-1,3,5-triazine) was synthesized using the following
reaction scheme: 18
[0325] The following were added, from first to last, to a 2 neck
round bottom flask equipped with a magnetic stirring bar, a reflux
condenser, an argon inlet and a rubber septum:
[0326] 4.83 g of Compound A,
[0327] 30 ml of xylene,
[0328] 3.0 ml of ethanolamine and
[0329] 122 mg of 4-dimethylaminopyridine ("DMAP") as catalyst.
[0330] The reaction mixture was heated to reflux and refluxed for 5
h; at this time, tlc analysis indicated the presence of Compound B
product and no starting Copound A material. The reaction mixture
was cooled to room temperature and diluted with hexane. The
precipitate thus formed was filtered then washed with hexane. The
precipitate was further purified by stirring with methanol,
filtered, then dried under reduced pressure to give 4.9 g of a
substantially pure product determined to be Compound B by .sup.1H
NMR, .sup.13C NMR and mass spectroscopy.
[0331] Preparation of Compound C
[0332]
4-[4,6-Bis(2'4'-dimethylphenyl)-1,3,5-triazin-2-yl]-3-hydroxyphenox-
yacetic acid, N, N-bis(2-hydroxyethyl)amide (Compound "C"), also
known as
2-[2-hydroxy-4-(N,N-bis-hydroxyethyl)-methanamidooxy)phenyl]-4,6-bis(2,4--
dimethylphenyl)-1,3,5-triazine) was synthesized using the following
reaction scheme: 19
[0333] The following were added, from first to last, to a 2 neck
round bottom flask equipped with a magnetic stirring bar, a reflux
condenser, an argon inlet and a glass stopper:
[0334] 966 mg of Compound A,
[0335] 10 ml of xylene,
[0336] 460 mg of diethanolamine and
[0337] 25 mg DMAP catalyst.
[0338] The reaction mixture was heated to reflux and refluxed for
20 h; at this time, tic analysis indicated the presence of Compound
C product and no starting Compound A material. The reaction mixture
was cooled to room temperature and filtered as described above,
redissolved in methylene chloride and precipitated by adding
hexane. The precipitates thus formed were filtered, washed with
hexane and dried under reduced pressure to give 1.0 g of a
substantially pure product determined to be Compound C by .sup.1H
NMR, .sup.13C NMR and mass spectroscopy.
[0339] Preparation of Compound D
[0340]
4-[4,6-Bis(2'4'-dimethylphenyl)-1,3,5-triazin-2-yl]-3-hydroxyphenox-
yacetic acid, N-ethyl-N-(2-hydroxyethyl)amide (Compound "D"), also
known as
2-[2-hydroxy-4-(N-ethyl-N-(2-hydroxyethyl)-methanamidooxy)phenyl]-4,6--
bis(2,4-dimethylphenyl)- 1,3,5-triazine) was synthesized using the
following reaction scheme: 20
[0341] The following were added, from first to last, to a 2 neck
round bottom flask equipped with a magnetic stirring bar, a reflux
condenser, an argon inlet and a glass stopper:
[0342] 9.66 g of Compound A,
[0343] 60 ml of xylene,
[0344] 4.9 ml of N-ethylethanolamine and
[0345] 244 mg of DMAP catalyst.
[0346] The reaction mixture was heated to reflux and refluxed for 8
h; at this time, tlc analysis indicated the presence of the
Compound D product and no starting Compound A material. The
reaction mixture was cooled to room temperature and filtered as
described above, redissolved in methylene chloride and precipitated
by adding hexane. The precipitates thus formed were filtered,
washed with hexane and dried under reduced pressure to give 10.1 g
of a substantially pure product determined to be Compound D by
.sup.1H NMR, .sup.13C NMR and mass spectroscopy.
[0347] Preparation of Compound E
[0348]
4-[4,6-Bis(2'4'-dimethylphenyl)-1,3,5-triazin-2-yl]-3-hydroxyphenox-
yacetic acid, N-(n-butyl)-N-(2-hydroxyethyl)amide (Compound "E");
also known as
2-[2-hydroxy-4-(N-(n-butyl)-N(2-hydroxyethyl)-methanamidooxy)phe-
nyl]4,6-bis(2,4dimethylphenyl)-1,3,5-triazine) was synthesized
using the following reaction scheme: 21
[0349] The following were added, from first to last, to a 2 neck
round bottom flask equipped with a magnetic stirring bar, a reflux
condenser, an argon inlet and a glass stopper:
[0350] 4.83 g of Compound A,
[0351] 30 ml of xylene,
[0352] 1.75 g of n-butylethanolamine and
[0353] 122 mg of DMAP catalyst.
[0354] The reaction mixture was heated to reflux and refluxed for 6
h; at this time, tic analysis indicated the presence of the
Compound E product and no starting Compound A material. The
reaction mixture was cooled to room temperature and diluted with
hexane. The precipitates thus formed were filtered, stirred with
100 ml of methanol, filtered and dried under reduced pressure to
give 5.3 g of a substantially pure product determined to be
Compound E by .sup.1H NMR, .sup.13C NMR and mass spectroscopy.
[0355] Preparation of Compound F
[0356] The adduct of Compound E with
1-(2-isocyanopropyl)-3-propenylbenzen- e ("m-TMI") was prepared
using the following reaction scheme: 22
[0357] The following were added to a 2 neck round bottom flask
equipped with a magnetic stirring bar, a reflux condense, an argon
inlet and a glass stopper:
[0358] 5.55 g of Compound E,
[0359] 40 ml of xylene,
[0360] 2.01 g of m-TMI and
[0361] 75 mg of 1,3-diacetoxy-1,1,3,3-tetrabutyldistannoxane
("TK-1") catalyst.
[0362] The reaction mixture was heated for 6 h at 120.degree. C.;
at this time, tic analysis indicated the presence of the Compound F
product and no starting Compound E material. The reaction mixture
was cooled to room temperature and concentrated under reduced
pressure to give 7.5 g of crude product. An analytical sample,
prepared by purifying the crude product using column chromatography
over silica gel, was determined to be Compound F by .sup.1H NMR,
.sup.13C NMR and mass spectroscopy.
[0363] Preparation of Compound G
[0364]
2-{4-[4,6-bis(2'4'-dimethylphenyl)-1,3,5-triazin-2-yl]-3-hydroxyphe-
noxy}-eth-1-yl N-(meta-isopropenyl-.alpha.,.alpha.-dimethylbenyzl)
carbamate (Compound "G") was synthesized using the following
reaction scheme: 23
[0365] The following were added, from first to last, to a 2 neck
round bottom flask equipped with a magnetic stirring bar, a reflux
condenser, an argon inlet and a glass stopper:
[0366] 5.55 g of
2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(6-hydroxyethy-
loxy)phenyl]-1,3-5-triazine ("HET"),
[0367] 40 ml of xylene,
[0368] 4.02 g of m-TMI and
[0369] 120 mg of TK-1 catalyst.
[0370] The reaction mixture was heated for 6 h at 120.degree. C.;
at this time, tic analysis indicated the presence of the Compound G
product and no HET starting material. The reaction mixture was
cooled to room temperature and concentrated under reduced pressure
to give 12.95 g of crude product. An analytical sample, prepared by
purifying the crude product using column chromatography over silica
gel, was determined to be Compound G by .sup.1H NMR, .sup.13C NMR
and mass spectroscopy.
[0371] Preparation of Compound H
[0372]
6-{4-[4,6-Bis(2'4'-dimethylphenyl)-1,3,5-triazin-2-yl]-3-hydroxyphe-
noxy}-hex-1-yl N-(meta-isopropenyl-.alpha.,.alpha.-dimethylbenyzl)
carbamate (Compound "H") was synthesized using the following
reaction scheme: 24
[0373] The following were added, from first to last, to a 2 neck
round bottom flask equipped with a magnetic stirring bar, a reflux
condenser, an argon inlet and a glass stopper:
[0374] 4.97 g of
2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(6-hydroxyhexy-
loxy)phenyl]-1,3-5-triazine ("HHT"),
[0375] 40 ml of xylene,
[0376] 2.01 g of m-TMI and
[0377] 75 mg of TK-1 catalyst.
[0378] The reaction mixture was heated for 6 h at 120.degree. C.;
at this time, tic analysis indicated the presence of the Compound H
product and no starting HHT material. The reaction mixture was
cooled to room temperature and concentrated under reduced pressure
to give 7 g of crude product. An analytical sample, prepared by
purifying the crude product using column chromatography over silica
gel, was determined to be Compound H by .sup.1H NMR, .sup.13C NMR
and mass spectroscopy.
[0379] Preparation of Compound I
[0380]
6-{4-[4,6-Bis(2'4'-dimethylphenyl)-1,3,5-triazin-2-yl]-3-hydroxyphe-
noxy}-hex-1-yl carbamate)phenyl]-1,3,5-triazine (Compound "I"),
also known as
2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(6-carbamoyloxyhexyloxy)phe-
nyl]-1,3-5-triazine) was synthesized using the following reaction
scheme: 25
[0381] The following were added, from first to last, to a 250 ml
round-bottom flask equipped with a magnetic stir bar and a
distillation head connected to a distillation condenser:
[0382] 30.0 g of HHT (0.060 mol),
[0383] 36.2 g of methyl carbamate ("MEC", 0.48 mol),
[0384] 100 ml of toluene and
[0385] 0.26 g of TK-1 (0.43 mmol).
[0386] The mixture was heated for 3.5 hours at an oil-bath
temperature (ca. 135.degree. C.) such that slow distillation of ca.
50 ml of toluene/methanol occurred. The resulting mixture was
allowed to cool and the solid mass dissolved in 800 ml of
CHCI.sub.3. This solution was extracted eight times, each time with
220 ml of water, then extracted once with 220 ml of brine. The
organic layer was dried over magnesium sulfate, filtered and rotary
evaporated, giving a yellow solid. The solid was dissolved in
boiling acetone, cooled to room temperature and placed in a
refrigerator at -15.degree. C. for 1 day. The product, which
separated as a solid, was isolated by filtration and vacuum oven
dried for 18 hours at 47-53.degree. C. affording 94.4 g (89.4% of
theoretical yield) of Compound I as a pale yellow solid with a
melting point of 147-150.degree. C.
[0387] Preparation of Compound J
[0388]
4-[4,6-Bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-3-hydroxypenoxya-
cetic acid, N-(2-(2-hydroxyethoxy)ethyl)amide (Compound "J"), also
known as
2-[2-hydroxy-4-(N-(2-(2-hydroxyethoxy)ethyl)-methanamidooxy)phenyl]-4,-
6-bis(2,4-dimethylphenyl)-1,3,5-triazine was synthesized using the
following reaction scheme: 26
[0389] The following were added, from first to last, to a 2 neck
round bottom flask equipped with a magnetic stirring bar, a reflux
condenser, an argon inlet, and a rubber septum:
[0390] 50 g of Compound A,
[0391] 250 mL of xylene,
[0392] 21 g -2-(2-aminoethoxy)ethanol and
[0393] 0.9 g of DMAP catalyst.
[0394] The reaction mixture was heated to reflux. An additional
10.5 g of 2-(2-aminoethoxy)ethanol and 0.9 g DMAP was added during
the course of the reaction. After 34 hours at reflux, the reaction
mixture was allowed to cool to room temperature and diluted with
hexane. The precipitated material was filtered, washed with hexane
and dried under reduced pressure to give 56 g of a substantially
pure product determined to be Compound J on the basis of .sup.1H
NMR and mass spectroscopy.
[0395] Preparation of Compound K
[0396]
4-[4,6-Bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-3-hydroxypenoxya-
cetic acid, N-(2-acryloyloxy)ethyl)amide (Compound "K"), also known
as
2-[2[hydroxy-4-(N-(2-acryloyloxy)ethyl)-methanamidooxy)phenyl]-4,6-bis(2,-
4-dimethylphenyl)-1,3,5-triazine was synthesized using the
following reaction scheme: 27
[0397] The following were added, from first to last, to a 2 neck
round bottom flask equipped with a magnetic stirring bar, a reflux
condenser, an argon inlet, and a rubber septum:
[0398] 498 mg of Compound B,
[0399] 5 mL of pyridine, and
[0400] 250 mg of acrylic anhydride
[0401] The mixture was stirred at room temperature for 24 h, and
then poured onto crushed ice. The mixture was stirred for 1 hr, and
extracted with methylene chloride. The organic layer was washed
with water, dried over anhydrous sodium sulfate, filtered, and
concentrated under reduced pressure to give 450 mg of a
substantially pure product determined to be Compound K on the basis
of .sup.1H NMR and mass spectroscopy.
[0402] Alternate Procedure for the Preparation of Compound K
[0403] Compound K was also prepared by reaction of Compound B and
acrylic acid in xylenes at 130.degree. C. for 24 h. The reaction
mixture was then concentrated under reduced pressure. TLC analysis
showed the presence of Compound B as well as the formation of a new
spot that corresponded to Compound K (by direct comparison of TLC
retention times to an authentic sample prepared by the above
reaction of Compound B with acrylic anhydride).
[0404] Preparation of Compound L
[0405]
4-[4,6-Bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-3-hydroxypenoxya-
cetic acid, N-(n-butyl)-N-(2-acryloyloxy)ethyl)amide (Compound
"L"), also known as
2-[2-hydroxy-4-(N-(n-butyl)-N-(2-acryloyloxy)ethyl)-methanamidoo-
xy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine was
synthesized using the following reaction scheme: 28
[0406] The same procedure used for the preparation of Compound K
using acrylic anhydride was followed. The product was determined to
be substantially pure Compound L on the basis of .sup.1H-NMR
spectroscopy.
Example 1 and Comparative Example 1
Solubility
[0407] Compound E (the disubstituted amide) was compared against
Compound B (the mono substituted amide) for solubility in a 1:1:1
mixture of xylenes:methyl amyl ketone (MAK):propylene glycol methyl
ether acetate (PM acetate), which is a typical coatings solvent
mixture. The results are presented below in Table I:
1TABLE 1 Solubility of Amide-Containing Triazines in the Solvent
Mixture (1:1:1 Xylenes:MAK:PM Acetate) Concentration Solubility
Stabilizer (wt %) 23.degree. C. 50.degree. C. 5.degree. C. CEX1 (B)
5 No No No EX1 (E) 5 Yes Yes Yes EX1 (E) 10 Yes Yes Yes
[0408] As can be seen from these results, Compound E fully
dissolved in the solvent mixture even at 10 wt %, and did not
crystallize out of solution at 5 .degree. C. Compound B, on the
other hand, did not dissolve, even at 5 wt % and at 50.degree.
C.
Example 2 and Comparative Example 2
Compatibility
[0409] Compound E was again compared against Compound B, this time
for compatibility in the following resin formulation which is the
polyol component of a typical two-component acrylic urethane
clearcoat formulation:
2 100 parts Acrylic Resin - JONCRYL .RTM. CDX-588 (70% Solids)
(S.C. Johnson & Son, Inc., Racine, WI 5 parts - 1 part
Dibutyltin Dilaurate (T-12, Air Products, Catalyst Solution
Allentown, PA) 45 parts Solvent Mixture (1:1:1 xylenes:MAK:PM
Acetate) 1 part Hindered Amine Light Stabilizer (SANDUVOR .RTM.
S-3055, Clariant Corp., Charlotte, NC).
[0410] The results are presented below in Table 2.
3TABLE 2 Compatibility of Triazines with Acrylic Urethane Component
I Compatibility Stabilizer Conc. (wt %).sup.a 23.degree. C.
60.degree. C. 5.degree. C. CEX1 (B) 1 No No No EX1 (E) 1 Yes Yes
Yes EX1 (E) 2 Yes Yes Yes .sup.aBased on total resin solids in
final formulation (both components)
[0411] As can be seen from the results, Compound E was compatible
with the resin component as it fully dissolved even at 5.degree. C.
Compound B, on the other hand, was not compatible at either
5.degree. C., 23.degree. C. or 60.degree. C.
[0412] Addition of DESMODUR.RTM. N-3390 (Bayer Corp.) and an
additional 17 parts of the solvent mixture (a polyisocyanate
crosslinker component of a typical two-component acrylic urethane
clearcoat formulation) to the formulations set forth above did not
result in the dissolution of Compound B in the fully formulated
coating, nor did it adversely affect the compatibility of Compound
E with the fully formulated coating.
Example 3
Bonding of Compound E to Acrylic/Melamine Resin Matrix
[0413] Compound E was investigated to determine whether it forms a
chemical bond with the acrylic/melamine resin matrix during curing.
For this purpose, it was added to a clearcoat formulation and
coated onto a plastic substrate, as described below. Non-bondable
UV absorbers readily migrate from clearcoats into plastic
substrates upon curing the coating. An absorber which bonds to the
matrix should not migrate into the plastic substrate to any
significant extent.
[0414] The acrylic/melamine resin formulation utilized was as
follows:
[0415] 40.6 g JONCRYL.RTM. 510 acrylic resin (S. C. Johnson, Inc.
Racine, Wis.)
[0416] 17.5 g CYMEL.RTM. 303 crosslinker (Cytec Industries, Inc.,
West Paterson, N.J.)
[0417] 0.52 g CYCAT.RTM. 4040 catalyst (Cytec Industries, Inc.,
West Paterson, N.J.)
[0418] 10.0 g n-Butanol
[0419] 0.50 g DC 57 flow control agent
[0420] 8.0 g xylene
[0421] To this formulation was added 3% of Compound E based on
total resin solids.
[0422] The resulting coating was drawn onto plastic RIM substrates
(Dow SPECTRIM.RTM. 50) using a #58 cator rod and cured for 30
minutes at 135.degree. C. After cure, the coating and part of the
substrate were microtomed into 10 .mu.m thick slices parallel to
the coating surface. The microtome was a Reichert-Jung Polycut E
instrument. Each microtomed slice was mounted between two
microscope slides and its UV absorption spectrum measured using a
Perkin-Elmer Lambda 2 spectrophotometer. The absorbance per
micrometer sample thickness was determined at the prominent 340 nm
absorption band intrinsic to this UVA.
[0423] The results of the UV analysis were plotted as a function of
depth. The original coating surface in contact with the atmosphere
was located at 0 .mu.m. The coating/substrate interface was at
about 70 .mu.m below the surface. The total microtomed depth was
about 130 .mu.m. The plotted curve showed a steep drop of the
absorbance near the coating/substrate interface, indicating that
most of the Compound E molecules remained in the coating, and only
minor amounts migrated through the interface into the plastic
substrate. By measuring the area under the curve, the quantity of
Compound E remaining in the coatings and the fraction that migrated
into the substrates were estimated. The result is that about 95% of
the added Compound E remained in the coating, with only about 5%
migrating into the substrate.
[0424] For comparison, CYASORB.RTM. UV1164L (a non-bondable
triazine UV absorber available from Cytec Industries Inc.) was
found to migrate into RIM substrates. Under identical experimental
conditions (30 minutes cure at 135.degree. C.), 63% of the added
non-bondable triazine UVA migrated into the substrate and only 37%
was left in the coating.
Example 3A
Bonding of Compound E to a Polycarboxylic Acid
[0425] Adipic acid was chosen as a model compound to demonstrate
the bonding of Compound E to poly(carboxylic acid) resin.
[0426] The following were added to a 3 neck round bottom flask
equipped with a magnetic stirring bar, a Dean-Stark trap with a
condenser, a thermocouple, and a nitrogen inlet:
[0427] 1.0 g of Compound E
[0428] 140 mg of adipic acid
[0429] 20 mL of xylenes
[0430] The mixture was heated at reflux for 1.5 h. At this time
HPLC analysis indicated that Compound E had completely reacted to
give new compounds containing the tris-aryl-1,3,5-triazine
chromophore, as determined by HPLC analysis.
Comparative Example 3A
Bonding of HHT to a Polycarboxylic Acid: Preparation of Compound
M
[0431] 29
[0432] The following were added to a 3 neck round bottom flask
equipped with a magnetic stirring bar, a Dean-Stark trap with a
condenser, a thermocouple, and a nitrogen inlet:
[0433] 1.0 g of HTT
[0434] 161 mg of adipic acid
[0435] 20 mL of xylenes
[0436] The mixture was heated at reflux for 2.5 h. At this time
HPLC analysis indicated that HTT was unreacted.
[0437] Even after 73 hr. at reflux, there was only 14% conversion
of HTT (based on HPLC area percent measurements at 290 nm) to a
mixture of the diester (Compound M) plus the corresponding
monoester.
[0438] This experiment, along with Example 3A, demonstrates the
unique reactivity of the hydroxyalkyl amido substituted
tris-aryl-1,3,5-triazine of the present invention compared to other
current art hydroxyl substituted tris-aryl-1,3,5-triazines.
Example 4
Bonding of Compound E to Polyurethane Resin Matrix
[0439] Bonding of Compound E in a solvent based polyurethane
coating was confirmed by a second experiment. The solvent based
polyurethane coating used had the following formula:
[0440] 103 g JONCRYL.RTM. CDX-588 acrylic resin (68% solids) (S. C.
Johnson & Son, Inc., Racine, Wis.)
[0441] 33 g DESMODUR.RTM. N-3390 crosslinker (90% solids) (Bayer
Corp., Pittsburgh, Pa.)
[0442] 59 g 1:1:1 xylene:MAK:PM Acetate solvent mix
[0443] 5 g T-12 catalyst.
[0444] Compound E was added to this formulation at the 2%
level.
[0445] The coating was drawin onto a block copoly(ester-ether)
plastic substrate (HYTREL.RTM. DYM 100, available from E. I. duPont
de Nemours and Company) used for automotive applications, witha #58
cator rod. After cure at 135.degree. C. for 30 minutes, the coating
and part of the substrate were microtomed and the microtomed slices
extracted using supercritical fluid extraction. The extracts were
analyzed for Compound E using HPLC. No Compound E was detected in
the slices cut from the coating or from the substrate. This
indicates that Compound E was chemically bonded to the resin matrix
and, therefore, could not be extracted from the coating, and
further that no Compound E migrated into the plastic substrate.
Example 5
Demonstration of Bonding to Compound I to a Resin Matrix
[0446] A "two-layer" approach was used to determine whether
Compound I bonds to the polyurethane resin matrix of Example 4
during cure. In the two-layer technique, two coating layers of
identical composition were coated on a steel substrate, with
Compound I added to the top layer only in an amount of 2% based
upon the solids content of the coating. The bottom layer was drawn
onto the substrate using a #58 cator rod and partially cured at
120.degree. C. for 10 minutes. The top layer was drawn onto the
partially cured bottom layer using a #58 cator rod.
[0447] The bonding of Compound I was ascertained by using depth
profiling similar to that described in Example 3, with the coating
sample being microtomed into thin slices parallel to the coating
surface. Each slice was subsequently analyzed for its stabilizer
content using UV spectroscopy as in Example 3. Two different cure
conditions were evaluated, 30 minutes at 80.degree. C. and 30
minutes at 120.degree. C. The UV absorbances of the individual
microtomed slices as a function of depth from the surface in
contact with the atmosphere for both cure conditions were measured.
Compound I was completely absent from the bottom layer of the
two-layer coating cured at 80.degree. C. Only 5% of Compound I was
present in the bottom layer of the two-layer caoting cured at
120.degree. C.
Example 5A
[0448] Bonding of Compound E into a water-based polyurethane
coating was confirmed as follows. The water-based polyurethane
coating was as follows:
4 6.8 g Acrylic polyol (73% in PMAc*) 4.2 g Cythane .RTM. 3174 (74%
in butyl acetate; Cytec Industries, West Paterson, NJ) 0.35 g
Triethylamine 0.41 g T-12 dibutyltin dilaurate catalyst 12.0 g
Water 3.24 g Compound E (5% in MEK) *PMAc - propylene glycol
monomethyl ether acetate
[0449] To test the bondability of Compound E in the above
formulation, the two-layer method of Example 5 was used. The UV
absorbances of the individual microtomed slices as a function of
depth from the surface in contact with the atmosphere for both cure
conditions were measured. The interface between the two
polyurethane layers is at 50 .mu.m. At this interface the UV
absorbance of the top layer drops essentially to zero. No UV
absorbance is observed in the bottom layer demonstrating that
Compound E is effectively bound to the resin of the top coating.
The amount of Compound E which migrated during cure from the top
paint layer into the lower layer was insignificant.
Example 5B
[0450] The bonding of Compound E in the water-borne polyurethane
coating of Example 5A was confirmed in a second experiment. The
resin was coated onto a Hytrel.RTM. DYM 100 substrate. DYM 100 is a
polyester/polyether plastic used for interior automotive
applications. After cure at 125.degree. C./20' the coating and part
of the substrate were microtomed and the microtomed slices
extracted using supercritical fluid extraction. The extracts were
analyzed for Compound E using HPLC. Compound E was not detected in
any of the slices cut from the coating or from the substrate. Two
conclusions are drawn from this result. First, Compound E was
chemically bonded to the resin matrix, and therefore, could not be
extracted from the coating. Second, Compound E did not migrate into
the DYM 100 substrate.
Example 6
Accelerated Weathering Testing of Clear Coatings
[0451] Formation of Clear Coatings
[0452] Compounds D and E were formulated in clear coatings which
were applied to panels for accelerated weathering testing as
follows. Compound D or E (1% or 2% based on total resin solids)
and/or SANDUVOR.RTM. S-3055 HALS-type stabilizer (1% based on total
resin solids) were predissolved in the solvent mixutre (to a 5-10%
solids level) and added to the clear acrylic urethane formulation
given in Table 3 below. Components I and II were mixed just before
use. Cold roll steel panels measuring 4".times.12" and precoated
with an electro-coat primer ED505A and a white polyester acrylic
melamine base-coat #542AB839, obtained from ACT Laboratories, Inc.
(Hillsdale, Mich.) were coated with the clear coating formulations
of Table 3. The draw-down technique, using WC-60 WireCators.TM.
(Leneta Co., Hohokus, N.J.), was used to apply the clear coat to
the pre-coated panels. The clear coats were allowed to flash for 10
min at ambient temperature and cured for 30 min at 135.degree.
C.
5TABLE 3 Acrylic Urethane Clear Coat Formulation Raw Material
Supplier Amount Component I Composition: Acrylic Resin: JONCRYL
.RTM. CDX-588 S.C. Johnson & Son, Inc., 100 parts (70% Solids)
Racine, WI Catalyst Solution 5 parts Solvent Mixture 45 parts
Triazine UV Absorber 1 or 2 parts.sup.a SANDUVOR .RTM. S-33055
(HALS type Clariant Corp., Charlotte, NC 1 part.sup.b stabilizer)
Component II Composition: Isocyanate: DESMODUR .RTM. N-3390 (90%
Miles Inc., Pittsburgh, PA 33 parts Solids) Solvent Mixture 17
parts Catalyst Solution Composition: (2% Solids in Catalyst
Solution) Dibutyltin Dilaurate: T-12 Air Products, Allentown, PA 1
part Acetic Acid 4 parts Propylene Glycol Methyl Ether Acetate 45
parts (PM Acetate) Solvent Mixture: Xylenes 1 part PM Acetate 1
part Methyl Amyl Ketone (MAK) 1 part .sup.aAmount for 1% or for 2%
based on total resin solids .sup.bOptional - when utilized the
amount for 1% based on total resin solids
[0453] Accelerated weathering was carried out on the clear coating
formulations using a QUV device equipped with UVB-313 fluorescent
bulbs. The coated panels were subjected to accelerated weathering
under alternate cycles of (i) UV light at 70.degree. C. for 8 hours
and (ii) condensation with no UV light at 50.degree. C. for 4 hours
(ASTM G53, GM cycle). Specular properties such as gloss (200,
ASTMD523) and distinctness of image ("DOI") (Dorigon Meter
D47R-6FT, Hunter Associate Laboratory) and yellowing ("Delta b")
were measured as a function of weathering time.
[0454] The results for QUV exposure using Compounds D or E as the
sole stabilizer are presented below in Table 4. The results for QUV
exposure using Compounds D or E in combination with S-3055 HALS are
presented below in Table 5.
6TABLE 4 QUV Weathering (UVA Alone) Hours % Comp. % Comp. QUV D E
Gloss DOI b 0 -- -- 93.5 77.0 3.65 2 -- 95.5 85.2 3.81 -- 2 94.3
78.2 3.82 % Gloss % DOI Retention Retention Delta b 544 -- -- 100.5
94.8 5.93 2 -- 100.0 101.9 2.56 -- 2 100.7 101.5 2.45 1047 -- --
101.4 97.1 8.81 2 -- 100.9 102.6 3.36 -- 2 101.5 102.3 3.38 1449 --
-- 101.9 101.9 10.48 2 -- 100.6 104.0 3.91 -- 2 101.2 104.1 4.04
1984 -- -- 98.4 101.4 11.01 2 -- 98.4 103.2 4.48 -- 2 98.2 102.9
4.61 2486 -- -- 29.1 13.1 10.80 2 -- 94.9 103.3 5.01 -- 2 94.3
103.1 5.28 2989 -- -- fail fail fail 2 -- 86.5 99.6 5.37 -- 2 75.5
89.8 5.42
[0455]
7TABLE 5 QUV Weathering (UVA + HALS) Hours % Comp. % Comp. % QUV D
E HALS Gloss DOI b 0 -- -- 1 94.1 88.8 3.70 2 -- 1 94.6 85.1 3.86
-- 2 1 94.8 90.3 3.86 % Gloss % DOI Delta Retention Retention b 544
-- -- 1 100.0 101.1 2.94 2 -- 1 101.1 101.1 0.93 -- 2 1 100.1 100.0
0.87 1047 -- -- 1 101.7 100.6 3.80 2 -- 1 101.5 101.5 1.44 -- 2 1
101.6 100.3 1.43 1449 -- -- 1 101.1 101.2 4.47 2 -- 1 101.8 102.5
1.75 -- 2 1 101.5 101.1 1.74 1984 -- -- 1 100.3 101.1 5.44 2 -- 1
100.8 102.5 2.15 -- 2 1 100.4 100.8 2.11 2486 -- -- 1 97.4 99.0
6.89 2 -- 1 98.3 102.5 2.47 -- 2 1 98.2 100.9 2.51 2989 -- -- 1
88.4 98.5 8.13 2 -- 1 89.6 114.6 2.75 -- 2 1 89.7 101.0 2.66 3467
-- -- 1 39.7 13.5 7.72 2 -- 1 98.9 103.3 2.99 -- 2 1 96.7 100.9
2.98 3967 -- -- 1 24.5 15.0 8.08 2 -- 1 94.3 102.1 3.23 % Gloss %
DOI Delta Retention Retention b -- 2 1 87.7 96.5 3.33 4443 -- -- I
fail fail fail 2 -- 1 91.4 98.1 3.26 -- 2 1 74.1 76.0 3.52
Example 7
Weathering of Clear Coatings Comprising Compound G
[0456] Example 6 was repeated, except that Compound G was used in
place of Compounds D and E. The results for QUV exposure using
Compound G as the sole stabilizer, and in combination with a HALS,
are presented below in Table 6.
8TABLE 6 QUV Weathering (UVA alone and UVA + HALS) Hours QUV %
Comp. G % HALS Gloss DOI b 0 -- -- 94.2 80.0 4.11 2 -- 95.2 86.9
4.29 1 1 94.4 85.6 4.06 % Gloss % DOT Delta Retention Retention b
501 -- -- 101.6 101.5 5.18 2 -- 100.9 100.6 2.38 1 1 102.0 100.4
1.09 1004 -- -- 102.5 103.6 6.81 2 -- 101.9 100.5 3.13 1 1 102.8
100.5 1.76 1515 -- -- 98.0 104.0 9.13 2 -- 100.6 100.5 4.67 1 1
100.4 101.3 2.52 1998 -- -- 81.8 72.1 9.82 2 -- 92.0 96.3 5.31 1 1
99.5 95.4 2.66 2499 -- -- 57.0 44.0 8.05 2 -- 75.6 64.3 5.79 1 1
105.4 101.9 3.68 3003 -- -- fail fail fail 2 -- 51.8 30.3 6.12 1 1
95.3 100.4 3.78
Example 8
Weathering of Clear Coatings--Compound I
[0457] The effectiveness of the light stabilizer systems of the
following examples was determined by measuring the gloss and %
gloss retention (ASTM D523), and DOI and % DOl retention (Dorigon
Meter D47R-6FT, Hunter Associate Laboratory), of a coating after
exposure in a QUV accelerated weathering unit equipped with UVA-340
fluorescent bulbs.
[0458] Standard 4".times.12" steel test panels available from ACT
Laboratories, coated with a primer (ED11) and a white base coat
(DuPont 872AB839 white), were coated by drawing down with a #52
wire cator a clear coating as described below. The coated panel was
cured for 30 mm. at 135.degree. C.
[0459] The clear coating comprised the following basic
components:
9 27.10 parts JONCRYL .RTM. 510 thermosetting acrylic resin (80%
solids) (S.C. Johnson & Sons), 11.67 parts CYMEL .RTM. 303
amino resin crosslinking agent (Cytec Industries), 0.33 parts CYCAT
.RTM. 4040 toluene sulfonic acid catalyst (40% solids in
isopropanol) (Cytec Industries), 0.33 parts DC-57 silicone leveling
agent (10% solids) (Dow Corning), 5.33 parts xylene, and 6.67 parts
n-butanol.
[0460] Compound I was added to this clear coating in the amounts
set forth in the tables below (in wt % based upon solids).
[0461] The coated panels were then subject to accelerated
weathering under alternate cycles of (i) TV light at 70.degree. C.
for 8 hours and (ii) condensation with no UV light at 50.degree. C.
for 4 hours (ASTM G53, GM Cycle).
[0462] The results are presented in Table 7 below. As can be seen
from these results, the panels without Compound I began degrading
at an early stage in the exposure cycle, and failed in about half
the time of the panels containing Compound I.
10TABLE 7 QUV Weathering (UVA Alone) Hours QUV % Comp. I Gloss %
Ret. DOI % Ret. 1513 2 98.1 99.0 93.8 98.3 1 98.2 98.5 94.2 98.3 --
97.0 99.8 91.4 95.6 2498 2 97.7 98.6 93.4 97.9 1 97.8 98.1 93.7
97.8 -- 93.2 95.9 80.7 84.4 2999 2 99.3 100.2 92.9 97.4 1 99.7
100.0 93.5 97.6 -- 90.0 92.6 56.1 58.7 3501 2 98.0 98.9 92.5 97.0 1
99.8 100.1 93.4 97.5 -- 63.0 64.8 34.1 35.7 4005 2 96.0 96.9 92.2
96.6 1 97.3 97.6 93.2 97.3 -- 51.5 53.0 26.5 27.7 4508 2 96.4 97.3
91.2 95.6 1 97.1 97.4 92.9 97.0 -- fail fail fail fail 5516 2 91.6
92.4 89.0 93.3 1 85.7 86.0 79.4 82.9 -- fail fail fail fail 5996 2
84.5 85.3 84.7 88.8 1 76.6 76.8 71.5 74.6 -- fail fail fail fail
6496 2 72.1 72.8 69.9 73.3 1 59.9 60.1 60.4 63.0 -- fail fail fail
fail
Example 9
Weathering of Clear Coatings--Compound I--HALS
[0463] Example 8 was repeated, except Compound I was used in
combination with a HALS SANDOVUR.RTM. S-3058, Clariant Corp.). The
results are presented in Table 8 below.
11TABLE 8 QUV Weathering (UVA + HALS) Hours QUV % Comp. I % HALS
Gloss % Ret. DOI % Ret. 1513 2 1 99.2 99.4 96.5 98.9 1 0.5 97.8
98.0 94.8 98.9 -- 1 96.9 99.3 94.9 97.9 -- 0.5 97.8 100.4 93.7 97.6
2498 2 1 98.3 98.5 96.2 98.6 1 0.5 99.1 99.3 94.5 98.5 -- 1 97.9
100.3 94.5 97.5 -- 0.5 98.4 101.0 93.4 97.3 2999 2 1 100.7 100.9
95.9 98.3 1 0.5 101.1 101.3 93.7 97.7 -- 1 99.5 101.9 94.3 97.3 --
0.5 99.7 102.4 93.9 97.8 3501 2 1 100.1 100.3 95.6 98.0 1 0.5 97.8
98.9 94.0 98.0 -- 1 99.1 101.5 94.0 97.0 -- 0.5 99.1 101.7 93.0
96.9 4005 2 1 98.5 98.7 95.5 97.8 1 0.5 98.2 98.4 94.0 98.0 -- 1
97.7 100.1 92.5 95.5 -- 0.5 98.0 100.6 92.9 96.8 4508 2 1 99.3 99.5
95.2 97.5 1 0.5 98.8 99.0 94.1 98.1 -- 1 99.3 101.7 93.7 96.7 --
0.5 98.7 101.3 91.5 95.3 5516 2 1 98.4 98.6 94.6 96.9 1 0.5 96.4
96.6 93.4 97.4 -- 1 97.6 100.0 92.6 95.6 -- 0.5 92.9 95.4 74.4 77.5
5996 2 1 97.8 98.0 94.1 96.4 1 0.5 96.0 96.2 93.4 97.4 -- 1 96.8
99.2 92.0 94.9 -- 0.5 87.8 90.1 65.4 68.1 6496 2 1 97.0 97.2 94.6
95.9 1 0.5 95.7 975.9 93.0 97.0 -- 1 97.5 99.9 90.6 93.5 -- 0.5
79.8 81.9 55.8 58.1 7000 2 1 95.7 95.9 93.2 95.5 1 0.5 94.3 94.5
93.0 97.0 -- 1 93.4 95.7 83.8 86.5 -- 0.5 73.1 75.1 51.2 53.3 7502
2 1 93.8 94.0 93.0 95.3 1 0.5 92.9 93.1 92.8 96.8 -- 1 91.0 93.2
73.9 76.3 -- 0.5 62.6 64.3 46.8 48.8 8041 2 1 90.7 90.9 92.2 94.5 1
0.5 88.3 88.5 92.0 95.9 -- 1 69.0 70.7 50.7 52.3 -- 0.5 fail fail
fail fail 8540 2 1 90.3 90.5 91.8 94.1 1 0.5 86.4 86.6 91.5 95.4 --
1 64.1 65.7 45.6 47.1 -- 0.5 fail fail fail fail
Example 10
Weathering of Clear Coatings--Synergy of Compounds E and F with
HALS
[0464]
12TABLE 8 QUV Weathering (UVA + HALS) % % Hours Comp. Comp.
Exposure E F % HALS Gloss DOI b 0 -- -- -- 88.6 60.4 3.66 2 -- --
89.2 60.3 3.79 -- 2 -- 66.3 32.9 3.90 -- -- 2 88.5 56.7 3.74 1 -- 1
91.4 65.6 3.74 -- 1 1 88.5 63.0 3.77 % Gloss % DOI Delta Retention
Retention b 1997 -- -- -- 106.9 125.5 7.64 2 -- -- 102.8 112.1 3.46
-- 2 -- 110.0 115.5 3.27 -- -- 2 105.0 116.0 3.35 1 -- 1 104.0
108.2 2.38 -- 1 1 102.8 103.7 2.31 2507 -- -- -- 43.9 29.6 8.59 2
-- -- 95.1 101.2 3.88 -- 2 -- 100.5 87.5 3.71 -- -- 2 101.7 119.6
4.20 1 -- 1 100.4 118.3 2.79 -- 1 1 98.8 99.4 2.78 3012 -- -- --
fail fail fail 2 -- -- 70.0 56.7 4.99 -- 2 -- 90.3 58.1 4.52 -- --
2 104.7 116.9 5.55 1 -- 1 98.9 101.2 3.33 -- 1 1 96.8 99.0 3.39
3513 -- -- -- fail fail fail 2 -- -- 16.3 0.0 5.30 -- 2 -- 38.5
19.8 5.02 -- -- 2 102.1 127.5 6.42 1 -- 1 96.7 110.9 4.07 -- 1 1
97.1 103.0 4.06 4017 -- -- -- fail fail fail 2 -- -- 26.5 14.4 5.99
-- 2 -- 40.9 35.0 5.28 -- -- 2 28.5 35.9 5.51 1 -- 1 85.9 93.8 3.93
-- 1 1 83.8 87.0 4.06 4515 -- -- -- fail fail fail 2 -- -- fail
fail fail -- 2 -- fail fail fail -- -- 2 fail fail fail 1 -- 1 72.5
76.6 4.23 -- 1 1 59.7 64.9 4.18
[0465] The clear coating composition of Example 6 was used to
evaluate the performance of Compounds E and F, alone at 2%, and in
combination with a HALS, SANDUVOR.RTM. 3055 (1% of Compound E plus
1% of S-3055; and 1% of Compound G plus 1% of S-3055). These
coating compositions were weathered by QUV according to the method
of Example 6. The results are presented in Table 8.
[0466] The data show that not only do Compounds E and F extend the
lifetime of the coating compositions in terms of percent gloss
retention, percent DOI retention, and yellowing (delta b) compared
to the unstabilized composition, but that the combinations of HALS
plus Compounds E and F used at the same total concentrations as the
individual stabilizers when used alone (1% of each for 2% total
concentration) exhibit a synergistic effect on these
properties.
[0467] As can be seen from the results, the panels with Compound I
maintained high gloss and distinctness of image significantly
longer than the panels without such compound.
[0468] 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 of this invention as defined by
the appended claims.
* * * * *