U.S. patent application number 10/013885 was filed with the patent office on 2002-11-07 for amino- and hydroxysubstituted triphenyl-s-triazines as stabilizers.
Invention is credited to Luther, Helmut, Metzger, Georges, Michaelis, Peter, Reinehr, Dieter.
Application Number | 20020165298 10/013885 |
Document ID | / |
Family ID | 27268220 |
Filed Date | 2002-11-07 |
United States Patent
Application |
20020165298 |
Kind Code |
A1 |
Reinehr, Dieter ; et
al. |
November 7, 2002 |
Amino- and hydroxysubstituted triphenyl-s-triazines as
stabilizers
Abstract
The present invention provides compounds having the formula: 1
in which R is hydrogen, hydroxy, halogen, C.sub.1-C.sub.20alkyl,
C.sub.4-C.sub.12cycloalkyl, C.sub.2-C.sub.20alkenyl,
C.sub.2-C.sub.20alkynyl, C.sub.1-C.sub.20-alkoxy,
C.sub.4-C.sub.12cycloal- koxy, C.sub.2-C.sub.20alkenoxy,
C.sub.2-C.sub.20alkynoxy or C.sub.7-C.sub.13aralkyl; R.sub.1 and
R.sub.2, independently, are hydrogen, C.sub.1-C.sub.20alkyl,
C.sub.4-C.sub.12cycloalkyl, C.sub.7-C.sub.13 aralkyl,
--C(.dbd.O)-R.sub.4 (in which R.sub.4 is C.sub.1-C.sub.20alkyl,
C.sub.2-C.sub.20alkyl interrupted by 1 to 6 oxygen atoms,
hetero-substituted C.sub.1-C.sub.20alkyl, C.sub.4-C.sub.12cycloalk-
yl, C.sub.2.sub.20alkenyl, C.sub.2C.sub.20alkynyl,
C.sub.1-C.sub.20-alkoxy- , C.sub.4-C.sub.12cycloalkoxy,
C.sub.2-C.sub.20alkenoxy, C.sub.2alkynoxy, C.sub.6-C.sub.12 aryl,
C.sub.6-C.sub.12 aryloxy or C.sub.7C.sub.13 aralkyl), or
--C(.dbd.O)-NH-R.sub.1 in which R.sub.1 has its previous
significance; and R.sub.3 is hydrogen, halogen, hydroxy,
C.sub.1-C.sub.20alkyl, C.sub.4-C.sub.12cycloalkyl,
C.sub.2-C.sub.20alkenyl, C.sub.2-C.sub.20alkynyl,
C.sub.1-C.sub.20-alkoxy- , C.sub.4-C.sub.12-cycloalkoxy,
C.sub.2C.sub.20alkenoxy, C.sub.2-C.sub.20alkynoxy, phenyl,
C.sub.7-C.sub.13 aralkyl or --N(R.sub.1)(R.sub.2) in which R.sub.1
and R.sub.2 have their previous significance, or R.sub.1 and
R.sub.2 together form a C.sub.4-C.sub.12 membered ring. The new
triphenyltriazine compounds have improved absorption spectrum
characteristics and superior resistance to exposure to UV light,
relative to known triphenyltriazine compounds.
Inventors: |
Reinehr, Dieter; (Kandern,
DE) ; Metzger, Georges; (Moernach, FR) ;
Michaelis, Peter; (Geispitzen, FR) ; Luther,
Helmut; (Grenzach-Wyhlen, DE) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION
PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
27268220 |
Appl. No.: |
10/013885 |
Filed: |
December 11, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10013885 |
Dec 11, 2001 |
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09651615 |
Aug 30, 2000 |
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09651615 |
Aug 30, 2000 |
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09155560 |
Sep 30, 1998 |
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09155560 |
Sep 30, 1998 |
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PCT/EP97/01331 |
Mar 17, 1997 |
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Current U.S.
Class: |
524/100 ;
544/180 |
Current CPC
Class: |
Y10S 514/972 20130101;
C07D 251/24 20130101; A61K 2800/52 20130101; C07D 265/22 20130101;
A61K 31/785 20130101; A61K 8/4966 20130101; A61Q 17/04
20130101 |
Class at
Publication: |
524/100 ;
544/180 |
International
Class: |
C08K 005/34; C07D
251/00 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 2, 1996 |
GB |
9606970.3 |
Claims
1. A compound having the formula: 47in which R is hydrogen,
hydroxy, halogen, C.sub.1C.sub.20-alkyl,
C.sub.4-C.sub.12cycloalkyl, C.sub.2-C.sub.20alkenyl,
C.sub.2-C.sub.20alkynyl, C.sub.1-C.sub.20-alkoxy- ,
C.sub.4-C.sub.12cycloalkoxy, C.sub.2-C.sub.20alkenoxy,
C.sub.2-C.sub.20 alkynoxy or C.sub.7-C.sub.13aralkyl; R.sub.1 and
R.sub.2, independently, are hydrogen, C.sub.1-C.sub.20alkyl,
C.sub.4-C.sub.12cycloalkyl, C.sub.7-C.sub.13 aralkyl,
--C(.dbd.O)-R.sub.4 (in which R.sub.4 is C.sub.1-C.sub.20alkyl,
C.sub.2-C.sub.20alkyl interrupted by 1 to 6 oxygen atoms,
hetero-substituted C.sub.1-C.sub.20alkyl, C.sub.4-C.sub.12cycloalk-
yl, C.sub.2-C.sub.20alkenyl, C.sub.2-C.sub.20alkynyl,
C.sub.1-C.sub.20-alkoxy, C.sub.4-C.sub.12cycloalkoxy,
C.sub.2-C.sub.20alkenoxy, C.sub.2-C.sub.20alkynoxy,
C.sub.6-C.sub.12 aryl, C.sub.6-C.sub.12 aryloxy or C.sub.7-C.sub.13
aralkyl), or --C(.dbd.O)-NH-R.sub.1 in which R.sub.1 has its
previous significance; and R.sub.3 is hydrogen, halogen, hydroxy,
C.sub.1-C.sub.20alkyl, C.sub.4-C.sub.12cycloalkyl,
C.sub.2-C.sub.20alkenyl, C.sub.2-C.sub.20alkynyl,
C.sub.1-C.sub.20-alkoxy, C.sub.4-C.sub.12cycloal- koxy,
C.sub.2-C.sub.20alkenoxy, C.sub.2-C.sub.20alkynoxy, phenyl,
C.sub.7-C.sub.13 aralkyl or --N(R.sub.1)(R.sub.2) in which R.sub.1
and R.sub.2 have their previous significance, or R.sub.1 and
R.sub.2 together form a C.sub.4-C.sub.12 membered ring.
2. A compound according to claim 1 in which R is hydrogen, hydroxy,
halogen, C.sub.1-C.sub.20-alkyl or C.sub.1-C.sub.20-alkoxy; R.sub.1
and R.sub.2, independently, are hydrogen, C.sub.1-C.sub.20alkyl,
C.sub.7-C.sub.13 aralkyl, --C(.dbd.O)-R.sub.4 (in which R.sub.4 is
C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkyl interrupted by 1 to 6
oxygen atoms, C.sub.2-C.sub.20alkenyl, C.sub.6-C.sub.12 aryl or
C.sub.6-C.sub.12 aryloxy), or --C(.dbd.O)-NH-R.sub.1 in which
R.sub.1 has its previous significance; and R.sub.3 is hydrogen,
halogen, hydroxy, C.sub.1-C.sub.2alkyl, phenyl,
--N(R.sub.1)(R.sub.2) in which R.sub.1 and R.sub.2 have their
previous significance or R.sub.1 and R.sub.2 together form a
C.sub.4-C.sub.12 membered ring.
3. A compound according to claim 1 having the formula: 48in which R
is hydrogen or C.sub.1-C.sub.4alkoxy; either R.sub.1 and R.sub.2
are each hydrogen, or R.sub.1 is hydrogen and R.sub.2 is
--C(.dbd.O)-R.sub.4 in which R.sub.4 is C.sub.1-C.sub.20alkyl,
C.sub.2-C.sub.20alkenyl, C.sub.1-C.sub.20alkoxy, phenyl optionally
substituted with C.sub.1-C.sub.4alkoxy or
CH.sub.2-(OCH.sub.2CH.sub.2).sub.nCH.sub.3 in which n is an integer
from 1 to 5; and R.sub.3 is hydrogen, C.sub.1-C.sub.20alkyl,
hydroxy, C.sub.1-C.sub.4alkoxy or phenyl.
4. A compound according to claim 3 in which R is hydrogen or
methoxy; either R.sub.1 and R.sub.2 are each hydrogen, or R.sub.1
is hydrogen and R.sub.2 is
--CO--CH.sub.2-(OCH.sub.2CH.sub.2).sub.n-OCH.sub.3 in which n is an
integer from 1 to 5; and R.sub.3 is hydrogen,
C.sub.1-C.sub.20alkyl, hydroxy, methoxy or phenyl.
5. A compound according to claim 1 having the formula: 49in which
either R.sub.1 and R.sub.2 are each hydrogen, or R.sub.1 is
hydrogen and R.sub.2 is --C(.dbd.O)-R.sub.4 in which R.sub.4 is
C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.20alkenyl,
C.sub.1-C.sub.20alkoxy, phenyl optionally substituted with
C.sub.1-C.sub.4alkoxy or CH.sub.2-(OCH.sub.2CH.sub.2).su-
b.n-OCH.sub.3 in which n is an integer from 1 to 5; and R.sub.3 is
hydrogen, hydroxy, C.sub.1-C.sub.20alkyl, methoxy or phenyl.
6. A compound according to claim 5 in which either R.sub.1 and
R.sub.2 are each hydrogen, or R.sub.1 is hydrogen and R.sub.2 is
--CO--CH.sub.3; and R.sub.3 is hydrogen, methoxy or phenyl.
7. A composition comprising (A) an organic material which is
sensitive to damage by light, oxygen and/or heat, and (B) as
stabilizer, a compound according to any one of claims 1 to 3.
8. A composition according to claim 7 comprising from 0.01 to 15
parts by weight of component (B), per 100 parts by weight of
component (A).
9. A composition according to claim 7 or 8 comprising, in addition
to components (A) and (B), one or more further stabilizers or
further additives.
10. A composition according to any of claims 7 to 9 comprising, as
component (A), a synthetic organic polymer.
11. A composition according to any of claims 7 to 10 comprising, as
component (A), a thermoplastic polymer, a binder for coatings or a
photographic material.
12. A composition according to claim 9 comprising, as component
(A), a binder for coatings and, as additional component C), one or
more stabilizers selected from light stabilizers of the sterically
hindered amine and/or 2-hydroxyphenyl-2H-benzotriazole type.
13. A composition according to claim 12 in which component C) is
present in an amount of 0.05 to 5 parts by weight, per 100 parts by
weight of the binder.
14. A composition according to claim 7 in which the organic
material which is sensitive to damage by light, oxygen and/or heat
is an undyed, dyed or printed fibre material.
15. A method of increasing the sun protection factor of textile
fibre materials, which comprises applying to the fibre materials a
compound according to any one of claims 1 to 6, in an aqueous or
aqueous-organic solution, and then fixing this compound.
16. A cosmetic preparation comprising at least one compound
according to any one of claims 1 to 6 and a cosmetically acceptable
auxiliary.
17. A process for stabilizing organic material against damage by
light, oxygen and/or heat, which comprises adding to this material
a stabilizer comprising one or more compounds according to any one
of claims 1 to 6.
18. The use of a compound according to any one of claims 1 to 6 as
a sunscreen for the human skin.
19. A process for the production of a compound of formula (1A )
comprising reacting an o-hydroxybenzamide of formula: 50in which R
is as defined in claim 1, with a benzoyl chloride of formula: 51in
which R.sub.3 is as defined in claim 1, to produce a compound of
formula: 52in which R and R.sub.3 have their previous significance;
and the compound of formula (6) is then reacted with a benzamidine
having the formula: 53in which R, R.sub.1 and R.sub.2 are as
defined in claim 1, to produce a compound of formula (1A).
20. A process for the production of a compound of formula (1A )
comprising comprising reacting an o-hydroxybenzamide of formula (4)
as definedin claim 19 with a p-nitro-benzoyl chloride of formula:
54in which R.sub.3 is as defined in claim 1, to produce a compound
having the formula: 55in which R and R.sub.3 are as defined in
claim 1, then reacting the compound of formula (9) with a
benzamidine having the formula: 56in which R is as defined in claim
1, to produce a compound of formula: 57in which R and R.sub.3 are
as defined in claim 1, and finally hydrogenating the compound of
formula (11) to produce a compound of formula (1A).
21. A process for the production of a compound of formula (1) or
(1A) comprising reacting an o-hydroxybenzamide of formula (4) as
defined in claim 19 with a p-acylaminobenzoyl chloride having the
formula: 58in which R.sub.3 and R.sub.4 are as defined in claim 1,
to produce compounds having the formula: 59in which R, R.sub.3 and
R.sub.4 are as defined in claim 1, and finally reacting the
compound of formula (13) with a compound of formula (10) to produce
a compound of formula: 60in which R, R.sub.3 and R.sub.4 are as
defined in claim 1.
22. The compounds having the formula: 61in which R and R.sub.3 are
as defined in claim 1.
23. A process for the production of compounds having the formula
(6) as defined in claim 22 comprising reacting an
o-hydroxybenzamide of formula: 62in which R is as defined in claim
1, with a benzoyl chloride of formula: 63in which R.sub.3 is as
defined in claim 1, to produce a compound of formula (6).
24. A compound having the formula (9): 64in which R and R.sub.3 are
as defined in claim 1.
25. A process for the production of a compound of formula (9) as
defined in claim 24 comprising reacting an o-hydroxybenzamide of
formula (4) as defined in claim 19 with a p-nitro-benzoyl chloride
of formula: 65in which R.sub.3 is as defined in claim 1, to produce
a compound having the formula (9).
26. A compound having the formula (13): 66in which R, R.sub.3 and
R.sub.4 are as defined in claim 1.
27. A process for the production of a compound having the formula
(13) comprising reacting an o-hydroxybenzamide of formula (4) as
defined in claim 19 with a p-acylaminobenzoyl chloride having the
formula: 67in which R.sub.3 and R.sub.4 are as defined in claim 1,
to produce compounds having the formula(13).
Description
[0001] The present invention relates to new compounds and, in
particular, to new amino- or amido-substituted triazine compounds
having excellent absorption spectrum characteristics and good
resistance to exposure to UV light, and to the use of the new
compounds as UV absorbers.
[0002] If it is desired to increase the light stability of an
organic material, especially a coating, a light stabilizer is
usually added. A class of light stabilizers which is very
frequently employed comprises the UV absorbers, which protect the
material by absorbing the harmful radiation via chromophores. An
important group of UV absorbers is the triphenyltriazines, which
are described, e.g., in EP-A434 608, EP-A-520 938, U.S. Pat. No. 4
619 956, EP-A-483 488, EP-A-500 496, EP-A-502 816 and EP-A-506
615.
[0003] A new group of triphenyltriazine compounds has now been
found which have improved absorption spectrum characteristics and
superior resistance to exposure to UV light, relative to known
triphenyltriazine compounds.
[0004] According to the present invention, there are provided
compounds having the formula: 2
[0005] in which R is hydrogen, hydroxy, halogen,
C.sub.1-C.sub.20-alkyl, C.sub.4-C.sub.12cycloalkyl,
C.sub.2-C.sub.20alkenyl, C.sub.2-C.sub.20alkynyl,
C.sub.1-C.sub.20-alkoxy, C.sub.4-C.sub.12cycloal- koxy.
C.sub.2-C.sub.20alkenoxy, C.sub.2-C.sub.20alkynoxy or
C.sub.7-C.sub.13aralkyl, preferably hydrogen, hydroxy, halogen,
C.sub.1-C.sub.20-alkyl or C.sub.1-C.sub.20-alkoxy; R.sub.1 and
R.sub.2, independently, are hydrogen, C.sub.1-C.sub.20alkyl,
C.sub.4-C.sub.12cycloalkyl, C.sub.7-C.sub.13 aralkyl,
--C(.dbd.O)-R.sub.4 (in which R.sub.4 is C.sub.1-C.sub.20alkyl,
C.sub.2-C.sub.20alkyl interrupted by 1 to 6 oxygen atoms,
hetero-substituted C.sub.1-C.sub.20alkyl,
C.sub.4-C.sub.12cycloalkyl, C.sub.2-C.sub.20alkenyl,
C.sub.2-C.sub.20alkynyl, C.sub.1-C.sub.20-alkoxy- ,
C.sub.4-C.sub.12cycloalkoxy, C.sub.2-C.sub.20alkenoxy,
C.sub.2-C.sub.20alkynoxy, C.sub.6-C.sub.12 aryl, C.sub.6-C.sub.12
aryloxy or C.sub.7-C.sub.13 aralkyl), or --C(.dbd.O)-NH-R.sub.1 in
which R.sub.1 has its previous significance, preferably R.sub.1 and
R.sub.2, independently, are hydrogen, C.sub.1-C.sub.20alkyl,
C.sub.7-C.sub.13 aralkyl, --C(.dbd.O)-R.sub.4 (in which R.sub.4 is
C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkyl interrupted by 1 to 6
oxygen atoms, C.sub.2-C.sub.20alkenyl, C.sub.6-C.sub.12 aryl or
C.sub.6-C.sub.12 aryloxy), or --C(.dbd.O)-NH-R.sub.1 in which
R.sub.1 has its previous significance; and R.sub.3 is hydrogen,
halogen, hydroxy, C.sub.1-C.sub.20alkyl,
C.sub.4-C.sub.12cycloalkyl, C.sub.2-C.sub.20alkenyl,
C.sub.2-C.sub.20alkynyl, C.sub.1-C.sub.20-alkoxy- ,
C.sub.4-C.sub.12cycloalkoxy, C.sub.2-C.sub.20alkenoxy,
C.sub.2-C.sub.20alkynoxy, phenyl, C.sub.7-C.sub.13 aralkyl or
--N(R.sub.1)(R.sub.2) in which R.sub.1 and R.sub.2 have their
previous significance, or R.sub.1 and R.sub.2 together form a
C.sub.4-C.sub.12 membered ring, preferably R.sub.3 is hydrogen,
halogen, hydroxy, C.sub.1-C.sub.20alkyl, phenyl, --N(R,)(R.sub.2)
in which R.sub.1 and R.sub.2 have their previous significance or
R.sub.1 and R.sub.2 together form a C.sub.4-C.sub.12 membered
ring.
[0006] When R and/or R.sub.3 is halogen, such halogen substituents
are fluorine, bromine, iodine or, especially, chlorine
substituents.
[0007] C.sub.1-C.sub.20alkyl groups R, R.sub.1, R.sub.2, R.sub.3
and/or R.sub.4 may be branched or unbranched such as methyl, ethyl,
n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl,
2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl,
1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl,
1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,
2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl,
n-nonyl, n-decyl, n-undecyl, 1-methylundecyl, n-dodecyt,
1,1,3,3,5,5-hexamethylhexyl, n-tridecyl, n-tetradecyl,
n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl and
n-eicosyl.
[0008] C.sub.1-C.sub.20alkoxy groups R, R.sub.3 and R.sub.4 may be
branched or unbranched such as methoxy, ethoxy, n-propoxy,
isopropoxy, n-butoxy, sec-butoxy, isobutoxy, t-butoxy,
2-ethylbutoxy, n-pentoxy, isopentoxy, 1-methylpentoxy,
1,3-dimethylbutoxy, n-hexoxy, 1-methylhexoxy, n-heptoxy,
isoheptoxy, 1,1,3,3-tetramethylbutoxy, 1-methylheptoxy,
3-methylheptoxy, n-octoxy, 2-ethylhexoxy, 1,1,3-trimethylhexoxy,
1,1,3,3-tetramethylpentoxy, n-nonoxy, n-decoxy, n-undecoxy,
1-methylundecoxy, n-dodecoxy, 1,1,3,3,5,5-hexamethylhexoxy,
n-tridecoxy, n-tetradecoxy, n-pentadecoxy, n-hexadecoxy,
n-heptadecoxy, n-octadecoxy and n-eicosoxy, preferably methoxy,
ethoxy or propoxy groups, especially methoxy groups.
[0009] When R.sub.4 is C.sub.2-C.sub.20alkyl which is interrupted
by from 1 to 6 oxygen atoms, this group may be branched or
unbranched such as 3-oxabutyl, 3-oxapentyl, 3-oxahexyl, 3-oxaoctyl,
3-oxadecyl, 3-oxadodecyl, 3-oxatetradecyl, 3-oxahexadecyl,
3-oxaoctadecyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 3,6-dioxadecyl,
3,6-dioxadodecyl, 3,6-dioxatetradecyl, 3,6-dioxaheptadecyl,
3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 3,6,9-trioxadodecyl,
3,6,9-trioxatetradecyl, 3,6,9-trioxahexadecyl or
3,6,9-trioxadecaheptyl.
[0010] When R.sub.4 is C.sub.1-C.sub.20alkyl which is substituted
by a heterocyclic residue, it may be any of the
C.sub.1-C.sub.20alkyl groups listed above in relation to
C.sub.1-C.sub.20alkyl groups R.sub.1, R.sub.2, R.sub.3 and/or
R.sub.4, preferably methyl, ethyl or propyl groups, especially a
methyl group, substituted by a morpholinyl, piperidyl,
2,2,6,6-tetramethylpiperidyl, piperazinyl or N-methylpiperazinyl
residue.
[0011] When R.sub.4 is a C.sub.2-C.sub.20alkenyl group, it may be,
e.g., allyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl,
n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl,
ndodec-2-enyl, iso-dodecenyl, n-dodec-2-enyl or
n-octadec-4-enyl.
[0012] When R.sub.4 is a C.sub.6-C.sub.10aryl group, it is a
naphthyl or, preferably, a phenyl group.
[0013] C.sub.7-C.sub.20aralkyl groups R.sub.2 and/or R.sub.4 may be
naphthylalkyl groups but are preferably phenylalkyl groups.
Examples of C.sub.7-C.sub.20 phenylalkyl groups R.sub.2 and/or
R.sub.4 include benzyl, .alpha.-methylbenzyl,
.alpha.,.alpha.-dimethylbenzyl, phenylethyl, phenylpropyl,
phenyl-butyl, phenylpentyl, phenylhexyl, phenylheptyl, phenyloctyl,
phenyinonyl, phenyidecyl, phenyidodecyl and phenyltetradecyl.
[0014] C.sub.6-C.sub.10aryl groups R.sub.4 and
C.sub.7-C.sub.20aralkyl groups R.sub.2 and/or R.sub.4 may be
unsubstituted or may be substituted by one of more substituents.
Examples of such substituent groups include hydroxyl, --NH.sub.2,
--NHR.sub.1, --NR.sub.1R.sub.2 (in which R.sub.1 and R.sub.2 have
their previous significance), halogen, C.sub.1-C.sub.20alkyl,
C.sub.1-C.sub.20alkoxy, C.sub.2-C.sub.2kenyl,
C.sub.3-C.sub.20alkynyl, C.sub.6-C.sub.12aryl, sulfonyl, carboxyl,
(meth)acryloxy or (meth)acrylamino.
[0015] Preferred compounds according to the invention are those
having the formula: 3
[0016] in which R is hydrogen or C.sub.1-C.sub.4alkoxy, preferably
methoxy; either R.sub.1 and R.sub.2 are each hydrogen, or R.sub.1
is hydrogen and R.sub.2 is --C(.dbd.O)-R.sub.4 in which R.sub.4 is
C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkenyl,
C.sub.1-C.sub.20alkoxy, phenyl optionally substituted with
C.sub.1-C.sub.4alkoxy or CH.sub.2-(OCH.sub.2CH.sub.2)n-OCH.sub.3 in
which n is an integer from 1 to 5; and R.sub.3 is hydrogen,
C.sub.1-C.sub.2alkyl, C.sub.1-C.sub.4alkoxy or hydroxy; and in
which preferably R is hydrogen or methoxy; either R.sub.1 and
R.sub.2 are each hydrogen, or R.sub.1 is hydrogen and R.sub.2 is
--CO--CH.sub.2-(OCH.sub.2CH.sub.2).sub.n-OCH.sub.- 3 in which n is
an integer from 1 to 5; and R.sub.3 is hydrogen,
C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkenyl, hydroxy, methoxy,
phenyl or methoxy-substituted phenyl.
[0017] Particularly preferred compounds according to the invention
are those having the formula: 4
[0018] in which either R.sub.1 and R.sub.2 are each hydrogen, or
R.sub.1 is hydrogen and R.sub.2 is --C(.dbd.O)-R.sub.4 in which
R.sub.4 is C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.20alkenyl,
C.sub.1-C.sub.20alkoxy, phenyl optionally substituted with
C.sub.1-C.sub.4alkoxy or
CH.sub.2-(OCH.sub.2CH.sub.2).sub.n-OCH.sub.3 in which n is an
integer from 1 to 5; and R.sub.3 is hydrogen, hydroxy,
C.sub.1-C.sub.20alkyl, methoxy or phenyl; and in which preferably
either R.sub.1 and R.sub.2 are each hydrogen, or R.sub.1 is
hydrogen and R.sub.2 is --CO-CH.sub.3; and R.sub.3 is hydrogen,
methoxy or phenyl.
[0019] The new compounds of formula (1) or (1A) may be prepared by
any of several synthetic routes.
[0020] For example, an o-hydroxybenzamide of formula: 5
[0021] in which R has its previous significance, may be reacted
with a benzoyl chloride of formula: 6
[0022] in which R.sub.3 has its previous significance, to produce a
compound of formula: 7
[0023] in which R and R.sub.3 have their previous significance; and
the compound of formula (6) is then reacted with a benzamidine
having the formula: 8
[0024] in which R, R.sub.1 and R.sub.2 have their previous
significance, to produce a compound of formula (1A).
[0025] In a second synthetic route, an o-hydroxybenzamide of
formula (4) may be reacted with a p-nitro-benzoyl chloride of
formula: 9
[0026] in which R.sub.3 has its previous significance, to produce a
compound having the formula: 10
[0027] in which R and R.sub.3 have their previous significance,
then reacting the compound of formula (9) with a benzamidine having
the formula: 11
[0028] in which R has its previous significance, to produce a
compound of formula: 12
[0029] in which R and R.sub.3 have their previous significance, and
finally hydrogenating the compound of formula (11) to produce a
compound of formula (1A).
[0030] In a third synthetic method, for the production of specific
compounds of formula (1) or (1A), an o-hydroxybenzamide of formula
(4) may be reacted with a p-acylaminobenzoyl chloride having the
formula: 13
[0031] in which R.sub.3 and R.sub.4 have their previous
significance, to produce compounds having the formula: 14
[0032] in which R, R.sub.3 and R.sub.4 have their previous
significance, and finally reacting the compound of formula (13)
with a compound of formula (10) to produce a compound of formula:
15
[0033] in which R, R.sub.3 and R.sub.4 have their previous
significance.
[0034] The novel triazine compounds are very good UV absorbers and
are therefore useful as stabilizers for organic polymers,
especially coating materials, against damage thereto by light and
as light stabilizers for textile fibre materials.
[0035] Particular advantages of the novel compounds include their
surprisingly high absorption in the 300 to 400 nm region of the
electromagnetic spectrum. Material stabilized with the compounds
according to the invention features outstanding resistance to the
effects of weathering and light, and outstanding photostability of
the incorporated stabilizer.
[0036] The materials to be stabilized can be, for example, oils,
fats, waxes, cosmetics or biocides. A particularly interesting
application is in polymeric materials which are present in
plastics, rubbers, paints and other coating materials, photographic
material or adhesives. Examples of polymers and other substrates
which can be stabilized in this way are the following:
[0037] 1. Polymers of monoolefins and diolefins, for example
polypropylene, polyisobutylene, polybut-1-ene,
poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as
polymers of cycloolefins, for example of cyclopentene or
norbornene; furthermore polyethylene (which optionally can be
crosslinked), for example high density polyethylene (HDPE),
polyethylene of high density and high molecular mass (HDPE-HMW),
polyethylene of high density and ultra-high molecular mass
(HDPE-UHMW), medium density polyethylene (MDPE), low density
polyethylene (LDPE), linear low density polyethylene (LLDPE),
branched low density polyethylene (BLDPE).
[0038] Polyolefins, i.e. polymers of monoolefins exemplified in the
preceding paragraph, in particular polyethylene and polypropylene,
can be prepared by different, and especially by the following,
methods:
[0039] a) radical polymerization (normally under high pressure and
at elevated temperature); or
[0040] b) catalytic polymerization using a catalyst that normally
contains one or more metals of group IVb, Vb, VIb or VII of the
Periodic Table. These metals usually have one or more ligands, such
as oxides, halides, alcoholates, esters, ethers, amines, alkyls,
alkenyls and/or aryls that may be either .pi.-or
.sigma.-coordinated. These metal complexes may be in the free form
or fixed on substrates, for example on activated magnesium
chloride, titanium(III) chloride, alumina or silicon oxide. These
catalysts may be soluble or insoluble in the polymerization medium.
The catalysts can be activated by themselves in the polymerization
or further activators may be used, for example metal alkyls, metal
hydrides, metal alkyl halides, metal alkyl oxides or metal
alkyloxanes, the metals being elements of groups Ia, IIa and/or
IIIa of the Periodic Table. The activators may be modified, for
example, with further ester, ether, amine or silyl ether groups.
These catalyst systems are usually termed Phillips, Standard Oil
Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site
catalysts (SSC).
[0041] 2. Mixtures of the polymers mentioned under 1), for example
mixtures of polypropylene with polyisobutylene, polypropylene with
polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of
different types of polyethylene (for example LDPE/HDPE).
[0042] 3. Copolymers of monoolefins and diolefins with each other
or with other vinyl monomers, for example ethylene/propylene
copolymers, linear low density polyethylene (LLDPE) and mixtures
thereof with low density polyethylene (LDPE), propylene/but-1-ene
copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene
copolymers, ethylene/hexene copolymers, ethylene/methylpentene
copolymers, ethylene/heptene copolymers, ethylene/octene
copolymers, propylene/butadiene copolymers, isobutylene/isoprene
copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl
methacrylate copolymers, ethylene/vinyl acetate copolymers and
their copolymers with carbon monoxide or ethylene/acrylic acid
copolymers and their salts (ionomers) as well as terpolymers of
ethylene with propylene and a diene such as hexadiene,
dicyclopentadiene or ethylidene-norbornene; and mixtures of such
copolymers with one another and with polymers mentioned under 1),
for example polypropylene/ethylene-propylene copolymers,
LDPE/ethylene-vinyl acetate copolymers, LDPE/ethylene-acrylic acid
copolymers, LLDPE/ethylene-vinyl acetate copolymers,
LLDPE/ethylene-acrylic acid copolymers and alternating or random
polyalkylene/carbon monoxide copolymers and mixtures thereof with
other polymers, for example polyamides.
[0043] 4. Hydrocarbon resins (for example C.sub.5-C.sub.9)
including hydrogenated modifications thereof (e.g. tackifiers) and
mixtures of polyalkylenes and starch.
[0044] 5. Polystyrene poly-(p-methylstyrene),
poly-(a-methylstyrene).
[0045] 6. Copolymers of styrene or a-methylstyrene with dienes or
acrylic derivatives, for example styrene/butadiene,
styrene/acrylonitrile, styrene/alkyl methacrylate,
styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl
methacrylate, styrene/maleic anhydride,
styrene/acrylonitrile/methyl acrylate; mixtures of high impact
strength of styrene copolymers and another polymer, for example a
polyacrylate, a diene polymer or an ethylene/propylene/diene
terpolymer, and block copolymers of styrene such as
styrene/butadiene/styrene, styrene/isoprene/styrene,
styrene/ethylene/butylene/styrene or
styrene/ethylene/propylene/styrene.
[0046] 7. Graft copolymers of styrene or a-methylstyrene, for
example styrene on polybutadiene, styrene on polybutadiene-styrene
or polybutadiene-acrylonitrile copolymers, styrene and
acrylonitrile (or methacrylonitrile) on polybutadiene; styrene,
acrylonitrile and methyl methacrylate on polybutadiene; styrene and
maleic anhydride on polybutadiene; styrene, acrylonitrile and
maleic anhydride or maleimide on polybutadiene; styrene and
maleimide on polybutadiene, styrene and alkyl acrylates or alkyl
methacrylates on polybutadiene, styrene and acrylonitrile on
ethylene/propylene/diene terpolymers, styrene and acrylonitrile on
polyalkyl acrylates or polyalkyl methacrylates, styrene and
acrylonitrile on acrylate/butadiene copolymers, as well as mixtures
thereof with the copolymers mentioned under 6), for example the
copolymer mixtures known as ABS, MBS, ASA or AES polymers.
[0047] 8. Halogen-containing polymers such as poiychloroprene,
chlorinated rubber, chlorinated and brominated copolymer of
isobutylene-isoprene (halobutyl rubber), chlorinated or
sulfochlorinated polyethylene, copolymers of ethylene and
chlorinated ethylene, epichlorohydrin homo- and copolymers,
especially polymers of halogen-containing vinyl compounds, for
example polyvinyl chloride, polyvinylidene chloride, polyvinyl
fluoride; polyvinylidene fluoride; as well as copolymers thereof
such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl
acetate or vinylidene chloride/vinyl acetate.
[0048] 9. Polymers derived from .alpha.,.beta.-unsaturated acids
and derivatives thereof such as polyacrylates and
polymethacrylates, polymethyl methacrylates, polyacrylamides and
polyacrylonitriles, impact-modified with butyl acrylate.
[0049] 10. Copolymers of the monomers mentioned under 9) with each
other or with other unsaturated monomers, for example
acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate
copolymers, acrylonitrile/alkoxyalkyl acrylate copolymers,
acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl
methacrylate/butadiene terpolymers.
[0050] 11. Polymers derived from unsaturated alcohols and amines of
the acyl derivatives or acetals thereof, for example polyvinyl
alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate,
polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or
polyallyl melamine; as well as their copolymers with olefins
mentioned in point 1.
[0051] 12. Homopolymers and copolymers of cyclic ethers such as
polyalkylene glycols, polyethylene oxide, polypropylene oxide or
copolymers thereof with bisglycidyl ethers.
[0052] 13. Polyacetals such as polyoxymethylene and those
polyoxymethylenes which contain comonomers, for example ethylene
oxide; polyacetals modified with thermoplastic polyurethanes,
acrylates or MBS.
[0053] 14. Polyphenylene oxides and sulfides, and mixtures thereof
with styrene polymers or polyamides.
[0054] 15. Polyurethanes derived from hydroxyl-terminated
polyethers, polyesters and polybutadienes on the one hand and
aliphatic or aromatic polyisocyanates on the other, as well as
precursors thereof.
[0055] 16. Polyamides and copolyamides derived from diamines and
dicarboxylic acids and/or from aminocarboxylic acids or the
corresponding lactams, such as polyamide 4, polyamide 6, polyamide
6/5, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12,
aromatic polyamides starting from m-xylene, diamine and adipic
acid; polyamides prepared from hexamethylenediamine and isophthalic
and/or terephthalic acid and with or without an elastomer as
modifier, for example poly-2,4,4-trimethylhexamet- hylene
terephthalamide or poly-m-phenylene isophthalamide. Block
copolymers of the aforementioned polyamides with polyolefins,
olefin copolymers, ionomers or chemically bonded or grafted
elastomers; or with polyethers, e.g. with polyethylene glycol,
polypropylene glycol or polytetramethylene glycol. As well as
polyamides or copolyamides modified with EPDM or ABS; and
polyamides condensed during processing (RIM polyamide systems).
[0056] 17. Polyureas, polyimides, polyamide-imides,
polyetherimides, polyesterimides, polyhydantoins and
polybenzimidazoles.
[0057] 18. Polyesters derived from dicarboxylic acids and diols
and/or from hydroxycarboxylic acids or the corresponding lactones,
such as polyethylene terephthalate, polybutylene terephthalate,
poly-1,4-dimethylolcyclohexane terephthalates and
polyhydroxybenzoates, as well as block polyether esters derived
from hydroxyl-terminated polyethers; and also polyesters modified
with polycarbonates or MBS; and acid-modified polyesters.
[0058] 19. Polycarbonates and polyester carbonates.
[0059] 20. Polysulfones, polyether sulfones and polyether
ketones.
[0060] 21. Crosslinked polymers derived from aldehydes on the one
hand and phenols, urea or melamine on the other hand, such as
phenol/formaldehyde resins, urea/formaldehyde resins and
melamine/formaldehyde resins.
[0061] 22. Drying and non-drying alkyd resins.
[0062] 23. Unsaturated polyester resins derived from copolyesters
of saturated and unsaturated dicarboxylic acids with polyhydric
alcohols and vinyl compounds as crosslinking agents, and also
halogen-containing modifications thereof of low flammability.
[0063] 24. Crosslinkable acrylic resins derived from substituted
acrylates, for example from epoxy acrylates, urethane acrylates or
polyester acrylates.
[0064] 25. Alkyd resins, polyester resins and acrylate resins
crosslinked with melamine resins, urea resins, isocyanates,
isocyanurates, polyisocyanates or epoxy resins.
[0065] 26. Crosslinked epoxy resins derived from aliphatic,
cycloaliphatic, heterocyclic or aromatic glycidyl compounds, for
example products of bisphenol A diglycidyl ethers, bisphenol F
diglycidyl ethers, which are crosslinked by means of customary
hardeners, for example anhydrides or amines, with or without
accelerators.
[0066] 27. Natural polymers such as cellulose, rubber, gelatin and
chemically modified homologous derivatives thereof, for example
cellulose acetates, cellulose propionates and cellulose butyrates,
or the cellulose ethers such as methyl cellulose; as well as rosins
and derivatives.
[0067] 28. Blends of the aforementioned polymers (polyblends), for
example PP/EPDM, poly-amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS,
PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates,
POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POW/MBS,
PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HOPE, PA/PP, PA/PPO,
PBT/PC/ABS or PBT/PET/PC.
[0068] The invention therefore also relates to a composition
comprising
[0069] (A) an organic material which is sensitive to damage by
light, oxygen and/or heat, and
[0070] (B) as stabilizer, a compound of the formula (1) or
(1A).
[0071] The invention also relates to a process for stabilizing
organic material against damage by light, oxygen and/or heat, which
comprises adding thereto, as stabilizer, a compound of the formula
(1) or (1A), and to the use of the compound of the formula (1) or
(1A) for stabilizing organic material.
[0072] The amount of the stabilizer to be used depends on the
organic material to be stabilized and on the intended use of the
stabilized material. In general, the novel composition comprises
from 0.01 to 15 parts by weight, in particular from 0.05 to 10
parts by weight, especially from 0.1 to 5 parts by weight, of the
stabilizer (component B) per 100 parts by weight of component
(A).
[0073] The stabilizer (component (B)) can also be a mixture of two
or more compounds of the formula (1) or (1A). In addition to the
novel compounds, the novel compositions can also comprise other
stabilizers or other additives, for example antioxidants, further
light stabilizers, metal deactvators, phosphites or phosphonites.
Examples of these stabilizers are the following:
[0074] 1. Antioxidants
[0075] 1.1. Alkylated monophenols, for example
2,6-di-tert-butyl4-methylph- enol,
2-tert-butyl-4,6-di-methylphenol, 2,6-di-tert-butyl-4-ethylphenol,
2,6-di-tert-butyl-4-n-butylphenol,
2,6-di-tert-bu-tyl-4-isobutylphenol,
2,6-dicyclopentyl-4-methylphenol,
2-(.alpha.-methylcyclohexyl)-4,6-dimeth- yl-phenol,
2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,
2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are
linear or branched in the side chains, for example,
2,6-di-nonyl-4-methylphenol,
2,4-dimethyl-6-(1'-methylundec-1'-yl)phenol,
2,4-di-methyl-6-(1'-methylhe- ptadec-1'-yl)phenol,
2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures
thereof.
[0076] 1.2. Alkylithiomethylphenols, for example
2,4-dioctylthiomethyl-6-t- ert-butylphenol,
2,4-dioctylthiomethyl-6-methylphenol,
2,4-dioctylthiomethyl-6-ethylphenol,
2,6-di-dodecylthiomethyl-4-nonylphen- ol.
[0077] 1.3. Hydroquinones and alkylated hydroquinones, for example
2,6-di-tert-butyl-4-methoxy-phenol, 2,5-di-tert-butylhydroquinone,
2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octad-cyloxyphenol,
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,
bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
[0078] 1.4. Tocopherols, for example .alpha.-tocopherol,
.beta.-tocopherol, .gamma.-tocopherol, .delta.-tocopherol and
mixtures thereof (Vitamin E).
[0079] 1.5. Hydroxylated thiodiphenyl ethers, for example
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), 4,4'-bis(2,6-dimethyl-4-
-hydroxyphenyl)disulfide.
[0080] 1.6. Alkylidenebisphenols, for example
2,2'-methylenebis(6-tert-but- yl-4-methylphenol),
2,2'-methylenebis(6-tert-butyl-4ethylphenol),
2,2'-methylenebis[4-methyl-6-(.alpha.-methylcyclohexyl)-phenol],
2,2'-methylenebis(4-methyl-6-cyclohexylphenol),
2,2'-methylenebis(6-nonyl- -4-methylphenol),
2,2'-methylenebis(4,6-di-tert-butylphenol),
2,2'-ethylidenebis(4,6-di-tert-butyl-phenol),
2,2'-ethylidenebis(6-tert-b- utyl-4-isobutylphenol),
2,2'-methylenebis[6-(.alpha.-methylbenzyl)-4-nonyl- phenol],
2,2'-methylenebis[6-(.alpha.,.alpha.dimethylbenzyl)-4-nonylphenol-
], 4,4'-methylenebis(2,6-di-tert-butylphenol),
4,4'-methylenebis(6-tert-bu- tyl-2-methylphenol),
1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,
2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol,
1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane,
1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-n-dodecylmercaptobutane-
, ethylene glycol
bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate],
bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene,
bis[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphe-
nyl]terephthalate, 1,1-bis-(3,5-dimethyl2hydroxyphenyl)butane,
2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,
2,2-bis-(5-tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane2
1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
[0081] 1.7. O-, N- and S-benzyl compounds, for example
3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydi-benzyl 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,
isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
[0082] 1.8. Hydroxybenzylated malonates, for example
dioctadecyl-2,2-bis-(3,5-di-tert-butyl-2-hydroxybenzyl)-malonate,
di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)-malonate,
di-dodecylmercaptoethyl-2,2-bis-(3,5-di-tert-butyl-4-hydroxybenzyl)malona-
te,
bis[4-(1,1,3,3-te-tramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-h-
ydroxybenzyl)malonate.
[0083] 1.9. Aromatic hydroxybenzyl compounds, for example
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-tetrame-thylbenzene,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
[0084] 1.10. Triazine Compounds, for example
2,4-bis(octylmercapto)-6-(3,5-
-di-tert-butyl-4-hy-droxyanilino)-1,3,5-triazine,
2-octylmercapto-4,6-bis(-
3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazin-
e, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine,
1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate,
1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate,
2,4,6-tris(3,5-di-tert-butyl-4hydroxyphenylethyl)-1,3,5-triazine,
1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-tr-
iazine,
1,3,5-tris(3,5-dicyclohexyl4-hydroxybenzyl)isocyanurate.
[0085] 1.11. Benzglyhosphonates, for example
dimethyl-2,5-di-tert-butyl-4-- hydroxybenzylphospho-nate,
diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosph- onate,
dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the
calcium salt of the monoethyl ester of
3,5-di-tert-butyl-4-hydroxybenzylphosphoni- c acid.
[0086] 1.12. Acylaminophenols, for example 4-hydroxylauranilide,
4-hydroxystearanilide, octyl
N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbama- te.
[0087] 1.13. Esters of
.beta.-(3.5-di-tert-butyl4-hydroxyphenyl)propionic acid with mono-
or polyhydric alcohols, e.g. with 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,
trimethylol-propane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]- octane.
[0088] 1.14. Esters of
.beta.-(5-tert-butyl-4-hydroxy-3-methylphenyl)propi- onic acid with
mono- or polyhydric alcohols, e.g. with 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,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]o- ctane.
[0089] 1.15. Esters of
.beta.-(3.5-dicyclohexyl4-hydroxyphenyl)propionic acid with mono-
or polyhydric alcohols, e.g. with 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)isocyanura- te, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethytolpropane, 4-hydroxymethyl-1-phospha-2,6,7--
trioxabicyclo[2.2.2]octane.
[0090] 1.16. Esters of 3.5-di-tert-butyl-4-hydroxyphenyl acetic
acid with mono- or polyhydric alcohols, e.g. with 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)isocyanura- te, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane, 4-hydroxymethyl-1
-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0091] 1.17. Amides of
.beta.-(3.5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethyle-
nediamide,
N,N'-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)trimethyle-
nediamide,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hydrazide,
N,N'-bis[2-(3-[3,5i-tert-butyl-4-hydroxyphenyl]propionyloxy)ethy]oxamide
(Naugard.RTM. XL-1 supplied by Uniroyal).
[0092] 1.18. Ascorbic Acid (Vitamin C)
[0093] 1.19. Aminic antioxidants, for example
N,N'-di-isopropyl-p-phenylen- ediamine,
N,N'-di-sec-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpenty-
l)-p-phenylenediamine,
N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine- , N,
N'-bis(1-methylheptyl)-p-phenylenediamine,
N,N'-dicyclohexyl-p-phenyl- enediamine,
N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p-pheny-
lenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine,
N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine,
N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine,
N-cyclohexyl-N'-phenyl-p- -phenlenediamine,
4-(p-toluenesulfamoyl)diphenylamine,
N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine,
N-allyidiphenylamine, 4-isopropoxy-diphenylamine,
N-phenyl-1-naphthylamin- e, N-(4-tert-octylphenyl)-1-naphthylamine,
N-phenyl-2-naphthylamine, octylated diphenylamine, for example
p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol,
4-butyrylaminophenol, 4-nonanoylaminophenol,
4-dodecanoylamino-phenol, 4-octadecanoylaminophenol,
bis(4-methoxyphenyl)amine,
2,6-di-tert-butyl-4-dime-thylaminomethylphenol- ,
2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,
N,N,N',N'-tetramethyl4,4'-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-napohthylamine, a mixture of mono- and dialkylated
tert-butyl/tert-octyidiphenylamines, a mixture of mono and
dialkylated nonyidiphenylamines, a mixture of mono- and dialkylated
dodecyidiphenylamines, a mixture of mono- and dialkylated
isopropyl/isohexyldiphenylamines, a mixture of mono- und
dialkylated tert-butyidiphenylamines,
2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a
mixture of mono- und dialkylated tert-butyl/tert-octylph-
enothiazines, a mixture of mono- und dialkylated
tert-octyl-phe-nothiazine- s, N-allylphenothiazin,
N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene,
N,N-bis-(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine,
bis(2,2,6,6-tetramethylpiperid-4-yl)-sebacate,
2,2,6,6-tetramethylpiperid- in-4one,
2,2,6,6-tetramethylpiperidin-4-ol.
[0094] 2. UV Absorbers and Light Stabilisers
[0095] 2.1.2-(2'-Hydroxyohenyl)benzotriazoles, for example
2-(2'-hydroxy-5'-methylphenyl)-benzo-triazole,
2-(3',5'-di-tert-butyl-2'-- hydroxyphenyl)benzotriazole,
2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazo- le,
2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole,
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'-octyloxyphenyl)benzotriazole,
2-(3',5'di-tert-amyl-2'-hy- droxyphenyl)benzotriazole,
2-(3',5'-bis-(.alpha.,.alpha.-dimethylbenzyl)-2-
'-hydroxyphenyl)benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxyc-
arbonylethyl)phenyl)-5-chloro-benzotriazole,
2-(3'-tert-butyl-5'-[2-(2-eth-
ylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-b-
enzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)pheny-
l)benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)p-
henyl)benzotriazole
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-
-2'-hydroxyphenyl)benzotriazole,
2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)- benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)-
phenylbenzotriazole,
2,2'-methylene-bis-[4-(1,1,3,3-tetramethylbutyl)-6-be-
nzotriazole-2-ylphenol]; the transesterification product of
2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotd-
azole with polyethylene glycol 300;
[R--CH.sub.2CH.sub.2COO--CH.sub.2CH.su- b.2.sub.2 where
R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl,
2-[2'-hydroxy-3'-(.alpha.,.alpha.-dimethylbenzyl)-5'-(1,1,3,3-tetramethyl-
butyl)-phenyl]benzotriazole;
2-(2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5-
'-(.alpha.,.alpha.-dimethylbenzyl)-phenyl]benzotriazole.
[0096] 2.2.2-Hydroxybenzophenones, for example the 4-hydroxy,
4-methoxy, 4octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy,
4,2',4'-trihydroxy and Z-hydroxy-4,4dimethoxy derivatives.
[0097] 2.3. Esters of substituted and unsubstituted benzoic acids,
as for example 4-tertbutyl-phenyl salicylate, phenyl salicylate,
octylphenyl salicylate, dibenzoyl resorcinol,
bis(4-tert-butylben-zoyl) 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,
2-methyl-4,6-di-tert-butylphenyl
3,5-di-tert-butyl-4-hydroxybenzoate.
[0098] 2.4. Acrylates, for example ethyl
.alpha.cyano-.beta.,.beta.-diphen- ylacrylate, isooctyl
.alpha.-cyano-.beta.,.beta.-diphenylacrylate, methyl
.alpha.-carbomethoxycinnamate, methyl
.alpha.-cyano-.beta.-methyl-p-metho- xy-cinnamate, butyl
.alpha.-cyano-,-methyl-.beta.-methoxy-cinnamate, methyl
.alpha.-carbomethoxy-p-methoxycin-namate and
N-(.beta.-carbomethoxy-.beta.-cyanovinyl)-2-methylindoline.
[0099] 2.5. Nickel compounds, for example nickel complexes of
2,2'-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1
or 1:2 complex, with or without additional ligands such as
n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel
dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g.
the methyl or ethyl ester, of
4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes
of ketoximes, e.g. of 2-hydroxy-4-methylphenyl undecylketoxime,
nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole- , with or
without additional ligands.
[0100] 2.6. Sterically hindered amines, for example
bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,
bis(2,2,6,6-tetramethyl-4-p- iperidyl)succinate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,
bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)
n-butyl-3,5-di-tert-butyl-4-hydrox- ybenzylmalonate, the condensate
of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-- 4-hydroxypiperidine and
succinic acid, linear or cyclic condensates of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-triazine,
tris(2,2,6,6-tetramethyl-4- -piperidyl)nitrilotriacetate,
tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1-
,2,3,4-butane-tetracarboxylate,
1,1'-(1,2-ethanediyl)-bis-(3,3,5,5-tetrame- thylpiperazinone),
4-benzoyl-2,2,6,6-tetramethylpiperidine,
4-stearyloxy-2,2,6,6-tetramethylpiperidine,
bis(1,2,2,6,6-pentamethylpipe-
ridyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate,
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione,
bis(1-octyloxy-2,2,8,8-tetramethylpiperidyl)sebacate,
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or
cyclic condensates of
N,N'-bis-(2,2,6,6-tetramethyl4-piperidyl)hexamethylenediam- ine 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-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-tri-
azine and 1,2-bis-(3-aminopropylamino)ethane,
8-acetyl-3-dodecyl-7,7,9,9-t-
etramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,
3-dodecyl-1-(2,2,6,6-te-
tramethyl-4-piperidyl)pyrrolidin-2,5-dione,
3-dodecyl-1-(1,2,2,6,6-pentame-
thyl-4-piperidyl)pyrrolidine-2,5-dione, a mixture of
4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a
condensation product of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensation
product of 1,2-bis(3-aminopropylamino)ethane and
2,4,6-trichloro-1,3,5-triazine as well as
4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.
[136504-96-6]);
N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid,
N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid,
2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane,
a reaction product of
7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-- oxospiro
[4,5]decane und epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4--
piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,
N,N'-bis-formyl-N,N'-bis(-
2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, diester of
4-methoxy-methylene-malonic acid with
1,2,2,6,6-pentamethyl-4-hydroxypipe- ridine,
poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxa-
ne, reaction product of maleic acid
anhydride-.alpha.-olefin-copolymer with
2,2,6,6-tetramethyl-4-aminopiperidine or
1,2,2,6,6-pentamethyl-4-ami- nopiperidine.
[0101] 2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide,
2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide,
2,2'-didodecyloxy-5,5'-di-tert-butoxanilide,
2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide,
2-ethoxy-5-tert-butyl-2'-ethoxani- lide and its mixture with
2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and
p-methoxy-disubstituted oxanilides and mixtures of o- and
p-ethoxydisubstituted oxanilides.
[0102] 2.8.2-(2-Hydroxyphenyl)-1.3.5-triazines, for example
2,4,6-tris(2-hydroxy4-octyloxyphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-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-hydroxy4-pro-pyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazin-
e,
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-butyloxy-propoxy)phenyl]-4,6-bis(2,4-d-
imethyl)-1,3,5-triazine,
2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-propyloxy)ph-
enyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,
2-[4-(dodecyloxy/tridecyloxy-2-
-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triaz-
ine,
2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-di-
methylphenyl)-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-hydroxy-propoxy)phenyl]-1,3,5-triazine-
, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,
2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis-
(2,4-dimethylphenyl)-1,3,5-triazine, and/or a
2,4-bis(4-phenylphenyl)-6-ar- yl-triazine e.g. of WO 96/28431, such
as 2-[4-(dodecyloxy/tridecyloxy-2-hy-
droxypropoxy)-2-hydroxy-phenyl]-4,6-bis(4-phenylphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-octyloxyphenyl)4,6-bis(4-phenylphenyl)-1,3,5-triazine.
[0103] 3. Metal deactivators, for example 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,
N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
[0104] 4. Phosphites and phosphonites, for example 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) pentaerythritol
diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)-pentae-
rythritol diphosphite, diisodecyloxypentaerythritol diphosphite,
bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite,
bis(2,4,6-tris(tert-butylphenyl)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-di-benz[d,g]-1-
,3,2-dioxaphosphocin,
6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[-
d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)
methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl
phosphite, 2,2',2"
-nitrilo[triethyltris(3,3',5,5'-tetra-tert-butyl-1,1
'-biphenyl-2,2'-diyl)phosphite],
2-ethylhexyl(3,3',5,5'-tetra-tert-butyl-- 1,1
'-biphenyl-2,2'diyl)phosphite.
[0105] Especially preferred are the following phosphites:
[0106] Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos.RTM. 168,
Ciba-Geigy), tris(nonylphenyl) phosphite, 16
[0107] 5. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,
N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,
N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxyamine,
N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,
N-hexadecyl-N-octadecylhydroxylamine,
N-heptadecyl-N-octadecylhydroxylami- ne, N,N-dialkylhydroxylamine
derived from hydrogenated tallow amine.
[0108] 6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone,
N-ethyl-alpha-methyl-nitrone, N-octyl-aipha-heptyi-nitrone,
N-lauryl-alpha-undecyl-nitrone, N-tetradecyl-alpha-tridcyl-nitrone,
N-hexadecyl-alpha-pentadecyl-nitrone,
N-octadecyl-alpha-heptadecyl-nitron- e,
N-hexadecyl-alpha-heptadecyl-nitrone,
N-ocatadecyl-alpha-pentadecyl-nit- rone,
N-heptadecyl-alpha-heptadecyl-nitrone,
N-octadecyl-alpha-hexadecyl-n- itrone, nitrone derived from
N,N-dialkylhy-droxylamine derived from hydrogenated tallow
amine.
[0109] 7. Thiosynergits, for example, dilauryl thiodipropionate or
distearyl thiodipropionate.
[0110] 8. Peroxide scavengers, for example esters of
.beta.-thiodipropionic acid, for example the lauryl, stearyl,
myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt
of 2-mercaptobenzimidazole, zinc dibutyidithiocarbamate,
dioctadecyl disulfide, pentaerythritol
tetrakis(.beta.-dodecylmercapto)propionate.
[0111] 9. Polyamide stabilisers, for example, copper salts in
combination with iodides and/or phosphorus compounds and salts of
divalent manganese.
[0112] 10. Basic co-stabilisers, for example, melamine,
polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea
derivatives, hydrazine derivatives, amines, polyamides,
polyurethanes, alkali metal salts and alkaline earth metal salts of
higher fatty acids for example calcium stearate, zinc stearate,
magnesium behenate, magnesium stearate, sodium ricinoleate and
potassium palmitate, antimony pyrocatecholate or zink
pyrocatecholate.
[0113] 11. Nucleating agents, for example, inorganic substances
such as talcum, metal oxides such as titanium dioxide or magnesium
oxide, phosphates, carbonates or sulfates of, preferably, alkaline
earth metals; organic compounds such as mono- or polycarboxylic
acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic
acid, diphenylacetic acid, sodium succinate or sodium benzoate;
polymeric compounds such as ionic copolymers (ionomers).
[0114] 12. Fillers and reinforcing agents, for example, calcium
carbonate, silicates, glass fibres, glass bulbs, asbestos, talc,
kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon
black, graphite, wood flour and flours or fibers of other natural
products, synthetic fibers.
[0115] 13. Other additives, for example, plasticisers, lubricants,
emulsifiers, pigments, rheology additives, catalysts, flow-control
agents, optical brighteners, flameproofing agents, antistatic
agents and blowing agents.
[0116] 14. Benzofuranones and indolinones, for example 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 or EP-A-0591102 or
3-[4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert-butyl-benzofuran-2-one,
5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,
3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one]-
, 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,
3-(4-acetoxy-3,5-dimethylphenyl)-5,7di-tert-butyl-benzofuran-2-one,
3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one,
3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,
3-(2,3-dimethylphenyl)-5,7di-tert-butyl-benzofuran-2-one.
[0117] The type and amount of the further stabilizers added is
determined by the type of substrate to be stabilized and on its
intended use; frequently, from 0.1 to 5% by weight, based on the
polymer to be stabilized, are used.
[0118] The novel stabilizers can with particular advantage be
employed in compositions in which component (A) is a synthetic
organic polymer, especially a thermoplastic polymer, a binder for
coatings, for example paints, or a photographic material. Examples
of suitable thermoplastic polymers are polyolefins and polymers
comprising heteroatoms in the main chain. Preference is also given
to compositions in which component (A) is a thermoplastic polymer
comprising nitrogen, oxygen and/or sulphur, especially nitrogen or
oxygen, in the main chain.
[0119] Also of interest are compositions in which component (A) is
a polyolefin, for example polyethylene or polypropylene.
[0120] Incorporation into the organic polymers, for example into
the synthetic organic and, in particular, thermoplastic polymers,
can be carried out by addition of the novel triphenyl-substituted
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 latices. Another way of
incorporating the novel mixtures into polymers comprises adding
them before or during polymerization of the corresponding monomers
or before crosslinking.
[0121] The novel compounds can also be added to the plastics to be
stabilized in the form of a master batch which comprises these
compounds, for example, in a concentration of from 2.5 to 25% by
weight.
[0122] The novel compounds can expediently be incorporated by the
following methods:
[0123] as an emulsion or dispersion (for example to latices or
emulsion polymers)
[0124] as a dry mix during mixing of additional components or
polymer mixtures
[0125] by direct addition to the processing equipment (for example
extruders, internal mixers, etc.)
[0126] as a solution or melt.
[0127] The stabilized polymer compositions obtained in this way can
be converted into shaped articles, for example fibres, films,
tapes, sheets, sandwich boards, containers, pipes and other
profiles, by conventional methods, for example hot pressing,
spinning, extrusion or injection moulding.
[0128] The invention therefore additionally relates to the use of
the polymer composition according to the invention for the
production of a shaped article.
[0129] Use in multilayer systems is also of interest. In this case,
a novel polymer composition having a relatively high content of
novel stabilizer, for example, 5-15% by weight, is applied in a
thin film (10-100 gun) to a shaped article made from a polymer
containing little or no stabilizer of the formula (1) or (1A).
Application may be made at the same time as the shaping of the base
structure, for example by coextrusion. However, 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 5-15% by weight, in particular
5-10% by weight, of at least one compound of the formula (1) or
(1A).
[0130] 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
colour and gloss for a long time even when used outside.
[0131] Likewise of particular interest is the use of the novel
compounds of the formula (I) or (1A) as stabilizers for coatings,
for example for paints. The invention therefore also relates to
those compositions whose component (A) is a film-forming binder for
coatings.
[0132] The novel coating composition preferably comprises 0.01-10
parts by weight of (B), in particular 0.05-10 parts by weight of
(B), especially 0.1-5 parts by weight of (B), per 100 parts by
weight of solid binder (A).
[0133] Multilayer systems are possible here as well, where the
concentration of the novel stabilizer (component (8)) in the outer
layer can be relatively high, for example from 1 to 15 parts by
weight of (B), in particular 3-10 parts by weight of (B), per 100
parts by weight of solid binder (A).
[0134] 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.
[0135] The binder (component (A)) 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. In general, it is a
film-forming binder based on a thermoplastic or thermosetting
resin, predominantly on a thermosetting resin. Examples thereof are
alkyd, acrylic, polyester, phenolic, melamine, epoxy and
polyurethane resins and mixtures thereof.
[0136] Component (A) can be a cold-curable or hot-curable binder;
the addition of a curing catalyst may be advantageous. Suitable
catalysts which accelerate curing of the binder are described, for
example, in Ullmann's Encyclopedia of Industrial Chemistry, Vol.
A18, p.469, VCH Veriagsgesellschaft, Weinheim 1991.
[0137] Preference is given to coating compositions in which
component (A) is a binder comprising a functional acrylate resin
and a crosslinking agent.
[0138] Examples of coating compositions containing specific binders
are:
[0139] 1. paints based on cold- or hot-crosslinkable alkyd,
acrylate, polyester, epoxy or melamine resins or mixtures of such
resins, if desired with addition of a curing catalyst;
[0140] 2. two-component polyurethane paints based on
hydroxyl-containing acrylate, polyester or polyether resins and
aliphatic or aromatic isocyanates, isocyanurates or
polyisocyanates;
[0141] 3. one-component polyurethane paints based on blocked
isocyanates, isocyanurates or polyisocyanates which are deblocked
during baking;
[0142] 4. one-component polyurethane paints based on aliphatic or
aromatic urethanes or polyurethanes and hydroxyl group containing
acrylate, polyester or polyether resins;
[0143] 5. one-component polyurethane paints based on aliphatic or
aromatic urethaneacrylates or polyurethaneacrylates having free
amino groups within the urethane strukture and melamine resins or
polyether resins, if necessary with curing catalyst;
[0144] 6. two-component paints based on (poly)ketimines and
aliphatic or aromatic isocyanates, isocyanurates or
polyisocyanates;
[0145] 7. two-component paints based on (poly)ketimines and an
unsaturated acrylate resin or a polyacetoacetate resin or a
methacrylamidoglycolate methyl ester;
[0146] 8. two-component paints based on carboxyl- or
amino-containing polyacrylates and polyepoxides;
[0147] 9. two-component paints based on acrylate resins containing
anhydride groups and on a , polyhydroxy or polyamino component;
[0148] 10. two-component paints based on acrylate-containing
anhydrides and polyepoxides;
[0149] 11. 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;
[0150] 12. two-component paints based on unsaturated polyacrylates
and polymalonates;
[0151] 13. thermoplastic polyacrylate paints based on thermoplastic
acrylate resins or externally crosslinking acrylate resins in
combination with etherified melamine resins;
[0152] 14. paint systems based on siloxane-modified or
fluorine-modified acrylate resins.
[0153] In addition to components (A) and (B), the coating
composition according to the invention preferably comprises as
component (C) a light stabilizer of the sterically hindered amine
type, the 2-(2-hydroxyphenyl)-1,3,5-triazine and/or
2-hydroxyphenyl-2H-benzotriazol- e type, for example as mentioned
in the above list in sections 2.1, 2.6 and 2.8. Further examples
for light stabilizers of the 2-(2-hydroxyphenyl)-1,3,5-triazine
type advantageously to be added can be found e.g. in the
publications U.S. Pat. No. 4,619,956, EP-A-434608, U.S. Pat. Nos.
5,198,498, 5,322,868, 5,369,140, 5,298,067, WO-94/18278,
EP-A-704437, GB-A-2297091, WO-96128431. Of special technical
interest is the addition of the 2-(2-hydroxyphenyl)-1,3,5-triazines
and/or 2-hydroxyphenyl-2H-benzotriazoles, especially the
2-(2-hydroxyphenyl)-1,3- ,5-triazines.
[0154] To achieve maximum light stability, it is of particular
interest to add sterically hindered amines as set out in the
abovementioned list under 2.6. The invention therefore also relates
to a coating composition which in addition to components (A) and
(B) comprises as component (C) a light stabilizer of the sterically
hindered amine type.
[0155] This stabilizer is preferably a 2,2,6,6-tetraalkylpiperidine
derivative containing at least one group of the formula 17
[0156] in which G is hydrogen or methyl, especially hydrogen.
[0157] Component (C) is preferably used in an amount of 0.05-5
parts by weight per 100 parts by weight of the solid binder.
[0158] Examples of tetraalkylpiperidine derivatives which can be
used as component (C) are given in EP-A-356 677, pages 3-17,
sections a) to D). These sections of this EP-A are regarded as part
of the present description. It is particular expedient to employ
the following tetraalkylpiperidine derivatives:
[0159] bis(2,2,6,6-tetramethylpiperid4yl) succinate,
[0160] bis(2,2,6,6-tetramethylpiperid4-yl) sebacate,
[0161] bis(1,2,2,6,6-pentamethylpiperid4yl) sebacate,
[0162] di(1,2,2,6,6-pentamethylpiperidyl)
butyl-(3,5-di-tert-butyl-4-hydro- xybenzyl)malonate,
[0163] bis(1-octyloxy-2,2,6,6-tetramethylpiperid4yl) sebacate,
[0164] tetra(2,2,6,6-tetramethylpiperid-4-yl)
butane-1,2,3,4-tetracarboxyl- ate,
[0165] tetra(1,2,2,6,6-pentamethylpiperid-4-yl)
butane-1,2,3,4-tetracarbox- ylate,
[0166]
2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneic-
osane,
[0167]
8-acetyl-3dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane--
2,4dione,
[0168]
11-bis-(1,2,2,6,6-pentamethylpiperidine-4-yl-oxycarbonyl)-2-(4-meth-
oxyphenyl)-ethene,
[0169] or a compound of the formulae 18
[0170] in which m is 5-50.
[0171] Apart from components (A), (B) and, if used, (C), the
coating composition can also comprise further components, examples
being solvents, pigments, dyes, plasticizers, stabilizers,
thixotropic agents, drying catalysts and/or levelling agents.
Examples of possible components are those described in Ullmann's
Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pp.
429-471, VCH, Weinheim 1991.
[0172] Possible drying catalysts or curing catalysts are, for
example, organometallic compounds, amines, amino-containing resins
and/or phosphines. 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 metals Al, Ti or Zr,
or organometallic compounds such as organotin compounds, for
example.
[0173] 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.
[0174] Examples of metal chelates are the aluminium, titanium or
zirconium chelates of acetylacetone, ethyl acetylacetate,
salicylaldehyde, salicylaldoxime, o-hydroxyacetophenone or ethyl
trifluoroacetylacetate, and the alkoxides of these metals.
[0175] Examples of organotin compounds are dibutyltin oxide,
dibutyltin dilaurate or dibutyltin dioctoate.
[0176] Examples of amines are, in particular, tertiary amines, for
example tributylamine, trethanolamine, N-methyldiethanolamine,
N-dimethylethanolamine, N-ethylmorpholine, N-methylmorpholine or
diazabicyclooctane (triethylenediamine) and salts thereof. Further
examples are quaternary ammonium salts, for example
trimethylbenzylammonium chloride.
[0177] Amino-containing resins are simultaneously binder and curing
catalyst. Examples thereof are amino-containing acrylate
copolymers.
[0178] The curing catalyst used can also be a phosphine, for
example triphenylphosphine.
[0179] 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 abovementioned 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.
[0180] The coating compositions according to the invention can be
applied to any desired substrates, for example to metal, wood,
plastic or ceramic materials. They are preferably used as topcoat
in the finishing of automobiles. If the topcoat 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 layer.
[0181] 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.
[0182] Depending on the binder system, the coatings can be cured at
room temperature or by heating. The coatings are preferably cured
at 50-150.degree. C., and in the case of powder coatings even at
higher temperatures.
[0183] 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.
[0184] 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) or (1A) according to the invention. The paint is
preferably a topcoat for automobiles. The invention furthermore
relates to a process for stabilizing a coating based on organic
polymers against damage by light, oxygen and/or heat, which
comprises mixing with the coating composition a mixture comprising
a compound of the formula (I) or (1A); and to the use of mixtures
comprising a compound of the formula (I) or (1A) in coating
compositions as stabilizers against damage by light, oxygen and/or
heat.
[0185] 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 may be a high-solids paint or can be
solvent-free (e.g. a powder coating material). Powder coatings are,
for example, those described in Ullmann's Encyclopedia of
Industrial Chemistry, 5th Ed., A18, pages 438-444. The powder
coating material may also have the form of a powder-slurry
(dispersion of the powder preferably in water).
[0186] The pigments can be inorganic, organic or metallic pigments.
The novel coating compositions preferably contain no pigments and
are used as a clearcoat.
[0187] 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.
[0188] Preference is also given to the use of the novel compound of
the formula (1) or (1A) in photographic materials as stabilizer
against damage by light, especially by UV light. The invention
therefore also relates to a photographic material comprising a
compound of the formula (1) or (1A).
[0189] The compounds according to the invention can be used for
photosensitive materials of all kinds. For example, they can be
employed for colour paper, colour reversal paper, direct-positive
colour material, colour negative film, colour positive film, colour
reversal film and other materials. They are preferably used, inter
alia, for photosensitive colour material which comprises a reversal
substrate or which forms positives.
[0190] Furthermore, the novel compounds can be combined with other
UV absorbers, especially those which are dispersible in aqueous
gelatin, for example with hydroxyphenylbenzo-triazoles (cf. for
example U.S. Pat. Nos. 4,853,471, 4,973,702, 4,921,966 and
4,973,701), benzophenones, oxanilides, cyanoacrylates, salicylates,
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.
[0191] In particular, it is possible successfully to stabilize
photographic materials similar to those described in U.S. Pat. No.
4,518,686.
[0192] The invention therefore additionally relates to a
photographic material comprising, on support, a blue-sensitive, a
green-sensitive and/or a red-sensitive silver-halide emulsion layer
and, if desired, a protective layer, with a layer comprising a UV
absorber being arranged above the uppermost silver-halide emulsion
layer, wherein the UV absorber is a compound of the formula (1) or
(1A).
[0193] Preference is additionally given to photographic materials
which have a layer comprising a compound of the formula (1) or (1A)
above the uppermost silver-halide emulsion layer and/or between the
green- and red-sensitive silver-halide emulsion layers.
[0194] 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 (1) or (1A) must be
present at least in one layer.
[0195] The novel material preferably has gelatin interlayers
between the silver-halide emulsion layers.
[0196] Preference is given to photographic materials in which the
silver halide in the blue-sensitive, green-sensitive and/or
red-sensitive layer is silver chloride bromide comprising at least
90 mol % of silver chloride.
[0197] The compounds of the formula (1) or (1A) which are used in
accordance with the invention can be incorporated, alone or
together with the colour coupler and, if used, further additives,
into the colour photographic material 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.
[0198] Preferred colour couplers for use in the compositions of the
invention, examples of such compounds, further additives such as
colour 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-531
258 and EP-A-520 938, and in the literature cited therein.
[0199] The novel triazine compounds of the formula (1) or (1A) are
also suitable for use in a process for the photochemical
stabilization of undyed, dyed or printed fibre materials comprising
for example, silk, leather, wool, polyamide, polyester or
polyurethanes, and especially cellulose-containing fibre materials
of all kinds. This process forms a further aspect of the present
invention. Examples of such fibre materials are the natural
cellulose fibres, such as cotton, linen, jute and hemp, and also
viscose staple fibre and regenerated cellulose. Preferred textile
fibre materials are those of cotton or polyester. The novel
triphenyl-substituted triazine compounds are also suitable for the
photochemical stabilization of hydroxyl-containing fibres in blend
fabrics, for example blends of cotton with polyester fibres or
polyamide fibres. A further preferred area of application relates
to the blocking or reduction of the UV radiation which passes
through the abovementioned textile materials (UV cutting) and the
heightened sun protection which textile materials finished with a
novel compound offer to the human skin.
[0200] As textile fibre material to be treated, polyester- or
cellulose acetate-containing fibre materials are of particular
interest Examples of polyester fibres are, e.g., cellulose ester
fibres such as cellulose-21/2-acetate fibres and -triacetate
fibres, especially linear polyester fibres, optionally those
modified with acid. These polyester fibres may be obtained by
condensation of terephthalic acid with
1,4-bis(hydroxymethyl)-cyclohexane. Also of interest are fibres
from copolymers of terephthalic- and isophthalic acid and ethylene
glycol. Conventional polyester fibres in the textile industry are
particularly those comprising terephthalic acid and ethylene
glycol.
[0201] The textile material to be treated may also be a mixed
fabric of polyester fibres and other fibres, e.g.,
polyacrylonitrile/polyester-, polyamide/polyester-,
polyester/cotton-, polyester/viscose- or polyester/wool mixed
fibres, which may be discontinuously or continuously dyed or
printed in conventional manner.
[0202] The textile material can be used in various forms, for
example as piece goods such as knitted goods or fabrics, or as
yarns, e.g. on cheeses or warp beams.
[0203] Also very suitable for use in the process of the present
invention are textile fabrics which are used in the outerwear
garment sector and which are at least partly permeable to light. By
the use of such textiles, treated according to the process of the
present invention, skin tissue under the outerwear garment can be
protected against the damaging effects of UV-radiation. This
protective effect is known as UV-cutting and is manifested in that
the textile fibre material treated with a compound of formula (1)
or (1A) has a significantly increased Ultraviolet Protection Factor
(UPF), relative untreated textile fibe material.
[0204] The UPF is defined as the quotient of the dose of UV
radiation which damages protected skin to that which damages
unprotected skin. Accordingly, a UPF is also a measure of the
extent to which untreated fibre materials and fibre materials
treated with a novel compound of the formula (1) or (1A) are
permeable to UV radiation. The determination of the ultraviolet
protection factor of textile fibre materials is explained, for
example, in WO 94/04515 or in J. Soc. Cosmet. Chem. 40, 127-133
(1989) and can be carried out analogously thereto.
[0205] The compound of formula (1) or (1A) is added in an amount 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
fibre material.
[0206] The compounds of formula (1) or (1A) are only sparingly
soluble in water and are therefore applied in dispersed form. The
dispersions are formed by grinding the compounds of formula (1) or
(1A) in water, using an appropriate dispersing agent, with the aid,
e.g., of quartz spheres and a high-speed stirrer, until the
particle size required for applicational conditions has been
attained.
[0207] Examples of dispersing agents for the compounds of formula
(1) or (1A) include, e.g.:
[0208] acid esters or their salts of alkylene oxide adducts, such
as acid esters or their salts of a polyadduct of 4 to 40 mol
ethylene oxide on 1 mol of a phenol, or phosphoric acid esters of
the adducts of 6 to 30 mol ethylene oxide on 1 mol of
4-nonylphenol, on 1 mol of dinonylphenol or, especially, on 1 mol
of compounds which are produced by addition of 1 to 3 mol of
optionally substituted styrenes on to 1 mol of phenol;
[0209] polystyrene sulfonates;
[0210] fatty acid taurides;
[0211] alkylated diphenyl oxide-mono- or -di-sulfonates;
[0212] sulfonates of polycarboxylic acid esters;
[0213] addition products, converted into an acid ester with an
organic dicarboxylic acid or an inorganic polybasic acid, of 1 to
60, preferably 2 to 30 mol of ethylene oxide and/or propylene
oxide, on C.sub.8-C.sub.22-fatty amines, fatty amides, fatty acids
or fatty alcohols, or on C.sub.3-C.sub.6-alcohols having 3-6
hydroxy groups;
[0214] lignin sulfonates; and, particularly preferably
[0215] formaldehyde-condensation products such as condensation
products of lignin sulfonates and/or phenol and formaldehyde,
condensation products of formaldehyde with aromatic sulfonic acids,
such as condensation products of ditolylether sulfonates and
formaldehyde, condensation products of naphthalene sulfonic acids
and/or naphthol- or naphthylamine-sulfonic acids with formaldehyde,
condensation products of phenol sulfonic acids and/or sulfonated
dihydroxydiphenylsulfone and phenols or cresols with formaldehyde
and/or urea, as well as condensation products of
diphenyloxide-disulfonic acid derivatives with formaldehyde.
[0216] The textile material to be stabilised is preferably dyed
textile material, in particular textile material dyed with
dispersion dyes which are only slightly soluble in water. These
dyes are therefore present in the dye liquor predominately as a
fine dispersion. They may be of various dyes classes such as the
acridone-, azo-, anthraquinone-, coumarine-, methine-, perinone-,
naphthoquinoneimine-, quinophthalone-, styryl- or nitro-dye
classes. Mixtures of dispersion dyes can also be used according to
the present invention.
[0217] The dyeings are conducted from aqueous baths using a
continuous or discontinuous process. For discontinuous processes
(exhaustion processes), the liquor ratio can be selected from
within a wide range, e.g. 1:1 to 1:100, preferably 1:6 to 1:50. The
dyeing temperature is at least 50.degree. C. and is generally not
higher than 140.degree. C. Preferably the dyeing temperature is in
the range of from 80 to 135.degree. C.
[0218] For continuous processes, the dye baths, which can contain
further auxiliaries as well as the dyes, are applied to the piece
goods, for example by foularding, spraying or slop padding, and are
developed by thermofixing or high temperature steam processes.
[0219] Linear polyester fibres and cellulose fibres are preferably
dyed by the so-called high temperature processes, in closed and
pressure-resistant apparatus, at temperatures above 100.degree. C.,
preferably between 110 and 135.degree. C. and optionally under
pressure. Suitable closed vessels are, e.g., circulation apparatus,
such as cheese- or beam dyeing machines, winch vats, jet- or drum
dyeing machines, muff-dyeing apparatus, paddles or jiggers.
[0220] Cellulose-21/2-acetate fibres are preferably dyed at
temperatures of 80-85.degree. C.
[0221] If the compounds of formula (1) or (1A ) are added during
the dyeing application, they may be so applied that the fibre
material is first treated with them and the dyeing is then
conducted or, preferably, the fibre material is treated
simultaneously with the compounds of formula (1) or (1A ) and the
dyestuff in the dyebath. The application of the compounds of
formula (1) or (1A) can also be effected, however, subsequently on
the finished dyeing by means of thermofixing, e.g. at 190 to
230.degree. C. over a period of 30 seconds to 5 minutes. A
pretreatment with the compounds of formula (1) or (1A) is also
possible, whereby the textile material is simultaneously
surface-fixed.
[0222] The dye liquors can also contain further additives such as
dyeing auxiliaries, dispersing agents, carriers, wool protection-
and wetting agents, as well as de-foamers.
[0223] Moreover, the dye baths can contain mineral acids such as
sulfuric acid or phosphoric acid, or expediently organic acids such
as aliphatic carboxylic acids, e.g. formic acid, acetic acid,
oxalic acid or citric acid and/or salts such as ammonium acetate,
ammonium sulfate or sodium acetate. The acids are used particularly
for the adjustment of the pH-value of the dye bath used, the
pH-value lying preferably between 4 and 5.
[0224] Preferably, the fibre material is placed initially for 5
minutes at 40 to 80.degree. C. in the bath which contains the dye,
the stabiliser compounds of formula (1) or (1A ) and optionally
further additives, and which is adjusted to a pH-value of 4.5 to
5.5, the temperature is increased to 125 to 130.degree. C. over 10
to 20 minutes, and is further treated at this temperature for 15 to
90 minutes, preferably for 30 minutes.
[0225] The finishing of the dyeings is effected by cooling the dye
liquor to 50 to 80.degree. C., by rinsing the dyeings with water
and optionally by cleaning in conventional manner in alkaline
medium under reductive conditions. The dyeings are then rinsed
again and dried. If vat dyes are used for the cellulose component,
the goods are first treated with hydrosulfite at a pH-value of 6 to
12.5, in conventional manner, then treated with an oxidising agent
and finally washed out.
[0226] For the production of prints, the stabiliser compounds of
formula (1) or (1A), in the form of their aqueous dispersions, are
mixed with the printing pastes. The printing pastes contain e.g.
0.1 to 10%, preferably 0.1 to 5%, of the corresponding stabiliser
compounds of formula (1) or (1A), based on the weight of the
printing paste.
[0227] The amount of the dyestuff which is added to the printing
paste depends on the desired colour shade; generally, amounts of
0.01 to 15, preferably 0.02 to 10 weight %, based on the textile
material used, suffice.
[0228] In addition to the dyestuffs and the aqueous dispersions of
the stabiliser compounds of formula (1) or (1A), the printing
pastes also conveniently contain acid-stable thickeners, preferably
those of natural origin such as carob bean flour derivatives,
especially sodium alginate, either used alone or mixed with
modified cellulose, especially with preferably 20 to 25 weight % of
carboxymethylcellulose. The printing pastes can also contain acid
donors such as butyrolactone or sodium hydrogen phosphate,
stabilisers, sequestering agents, emulsifiers, water-insoluble
solvents, oxidising agents or deaerating agents.
[0229] Preferred stabilisers are formaldehye-liberating agents,
such as paraformaldehyde or trioxan, especially aqueous solutions
containing 30 40-weight % of formaldehyde; sequestering agents are
e.g. sodium nitrilotriacetate, sodium ethylenediarninotetraacetate,
especially sodium polymetaphosphate, in particular sodium
hexametaphosphate; emulsifiers are preferably adducts of an
alkylene oxide and a fatty alcohol, especially an adduct of oleyl
alcohol and ethylene oxide; water-insoluble solvents are preferably
high-boiling, saturated hydrocabons, especially paraffins having a
boiling range of 160 to 210.degree. C. (so-called white spirits);
oxidising agents are e.g. aromatic nitro-compounds, preferably
aromatic mono- or di-nitrocarboxylic acids or -sulfonic acids,
which are optionally used as alkylene oxide adducts, especially
nitrobenzene sulfonic acids; and deaerating agents are e.g.
high-boiling solvents, preferably turpentine oils, higher alcohols,
preferably C.sub.5-C.sub.10-alcohols, terpene alcohols or
deaerating agents based on mineral- and/or silicone oils,
especially commercial formulations of about 15 to 25 weight % of a
mineral- and silicone oil mixture and about 75 to 85 weight % of a
C.sub.8-C.sub.10-alcohol, such as 2-ethyl-n-hexanol.
[0230] For the printing of the fibre material, the printing paste
may be applied directly to the whole or part of the surface,
conveniently using printing machines of conventional construction,
typically ink-jet printing-, Vigoureux printing-, rotogravure
printing-, rotary screen printing and surface screen printing
machines.
[0231] After the printing, the fibre material may be dried at
temperatures up to 150.degree. C., preferably at 80 to 120.degree.
C.
[0232] The subsequent fixation of the fibre material is usually
effected by a heat treatment at temperatures of preferably 100 to
220.degree. C. The heat treatment is generally conducted using
superheated steam under pressure. Depending on the temperature, the
fixation may need form 20seconds to 10 minutes, preferably 4 to 8
minutes.
[0233] The prints are finished in conventional manner by rinsing
with water, followed by an optional additional cleaning in alkaline
medium under reductive conditions, e.g. using sodium dithionite. In
the latter case, the print dyeings are again rinsed, de-watered and
dried.
[0234] The textile fibres treated with the stabiliser compounds of
formula (1) or (1A) have good resistance to the damaging effects of
light, oxygen and heat. In particular, the stabilisation process
according to the present invention enables to provision of
polyester dyeings and prints which exhibit high lightfastness and
high resistance to sublimation. No specific pre- or after-treatment
of the fibre material is necessary with the stabilisation process
according to the present invention.
[0235] The UV absorbers according to the invention are suitable,
furthermore, as photoprotective agents in cosmetic
preparations.
[0236] The invention additionally relates, therefore, to a cosmetic
preparation comprising at least one compound of the formula (1) or
(1A) and cosmetically acceptable carriers or auxiliaries.
[0237] The novel cosmetic composition contains from 0.1 to 15% by
weight, preferably from 0.5 to 10% by weight, based on the overall
weight of the composition, of a UV absorber of the formula (1) or
(1A ) and a cosmetically acceptable auxiliary.
[0238] 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. Preferably, however, the sparingly water-soluble or
water-insoluble UV absorber of the formula (1) or (1A) is ground to
a mean particle size of 100-400 nm or less, for example by
wet-grinding in water using a suitable grinding aid and with the
addition of conventional auxiliary such as a surfactant or a
polymer or a mixture thereof the nanopigment so obtained is
incorporated into a conventional sun protection formulation. The
production of oil-in-water or water-in-oil emulsions containing one
or more pigments and in the presence of one or more oil- or
water-soluble UV absorber of the formula (1) or (1A) may be
conducted using known methods for the preparation of sun protection
emulsions.
[0239] 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.
[0240] 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.
[0241] 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.
[0242] 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 colourants.
[0243] The novel cosmetic formulations are notable for good
protection of human skin and/or hair against the damaging effect of
sunlight while at the same time providing for reliable tanning of
the skin.
[0244] The following Examples further illustrate the present
invention.
EXAMPLE 1
[0245] 19
[0246] 30 g of 4-methoxybenzoyl chloride are stirred with 12 g of
salicylamide for 30 minutes at 170.degree. C. A homogeneous oil is
produced which crystallises on cooling. The resulting crystalline
mass is treated with a suspension of 18.7 g of p-aminobenzamidine:2
HCl in 500 mls of methanol and with 40 g of a 30% aqueous sodium
methylate solution. The mixture so obtained is boiled under reflux
for an hour. After the resulting mixture is cooled and filtered,
there are obtained 25.8 g (79.5% theory) of a light-yellow product
having a melting point of 281-283.degree. C. The UV spectra reading
[.lambda..sub.max(nm)/.epsilon.- (L/mol.cm)] is 335/44195, as
determined in CHCl.sub.3 at 25.degree. C.
[0247] Elemental analysis of the compound having the formula (101)
and having the empirical formula C.sub.22H.sub.18N.sub.4O.sub.2
gives:
[0248] Req.% C71.37; H4.9; N15.13; O8.64. Found % C71.27; H4.99;
N15.7; O8.97. 20
[0249] The procedure described in Example 1 is repeated except that
4-methoxybenzoyl chloride is replaced by the equivalent amount of
benzoyl chloride. After working up, the compound of formula (102)
is obtained in a yield of 81% of theory and has a melting point of
293-294.degree. C. The UV spectra readings
[.lambda..sub.max(nm)/.epsilon.(L/mol.cm)] are 275/33035 and
348/34825, as determined in CHCl.sub.3 at 25.degree. C.
[0250] Elemental analysis of the compound having the formula (102)
and having the empirical formula C.sub.21H.sub.16N.sub.4O
gives:
[0251] Req.% C74.1; H4.74; N16.46; O4.7. Found % C74.0; H4.8;
N16.4; O4.8. 21
[0252] The procedure described in Example 1 is repeated except that
4methoxybenzoyl chloride is replaced by the equivalent amount of
biphenyl-4carboxylic acid chloride and salicylamide is replaced by
the equivalent amount of 4-methoxy salicylamide. After working up,
the compound of formula (103) is obtained in a yield of 66% of
theory and has a melting point of 244-247.degree. C. The UV spectra
reading [.lambda..sub.max(nm)/.epsilon.(L/mol.cm)] is 334/58810, as
determined in CHCl.sub.3 at 25.degree. C.
[0253] Elemental analysis of the compound having the formula (103)
and having the empirical formula C.sub.28H.sub.22N.sub.4O.sub.2
gives:
[0254] Req.% C75.32; H4.97; N12.55; O7.17. Found % C74.97; H5.05;
N12.39; O7.62. 22
[0255] The procedure described in Example 1 is repeated except that
4methoxybenzoyl chloride is replaced by the equivalent amount of
salicylic acid chloride. After working up, the compound of formula
(104) is obtained in a yield of 91% of theory and has a melting
point of 327-328.degree. C.
[0256] Elemental analysis of the compound having the formula (104)
and having the empirical formula C.sub.21,H.sub.16N.sub.4O.sub.2
gives:
[0257] Req.% C70.78; H4.53; N1.5.72; 8.98. Found % C70.67; H4.58;
N15.72; O9.0. 23
[0258] The procedure described in Example 1 is repeated except that
salicylamide is replaced by the equivalent amount of
4-methoxysalicylamide. After working up, the compound of formula
(105) is obtained in a yield of 69% of theory and has a melting
point of 223-227.degree. C.
[0259] Elemental analysis of the compound having the formula (105)
and having the empirical formula C.sub.23H.sub.20N.sub.4O.sub.3
gives:
[0260] Req.% C68.99; H5.03; N13.99; O11.99. Found % C69.06; H5.08;
N14.02; O11.84.
Example 5
[0261] 24
[0262] The procedure described in Example 1 is repeated except that
4-methoxybenzoyl chloride is replaced by the equivalent amount of
4octylbenzoyl chloride. After working up, the compound of formula
(106) is obtained in a yield of 69.5% of theory and has a melting
point of 184-185.degree. C.
[0263] Elemental analysis of the compound having the formula (106)
and having the empirical formula C.sub.29H.sub.32N.sub.4O
gives:
[0264] Req.% C76.96; H7.13; N12.38; O3.54. Found % C76.97; H7.11;
N12.39; O3.53.
Example 6
[0265] 25
[0266] 1 g of the compound of formula (101) in 15 mls of carbon
tetrachloride is boiled under reflux for 30 minutes with 0.4 g of
pyridine and 0.81 g of 2-ethylhexanoyl chloride. After filtering
off the reaction mixture, there are obtained 1.08 g of a light
beige crystalline product of formula (107) in a yield of 73% of
theory and having melting point of 221-223.degree. C.
[0267] Elemental analysis of the compound having the formula (107)
and having the empirical formula C.sub.30H.sub.32N.sub.4O.sub.3
gives:
[0268] Req.% C72.27; H6.51; N11.24; O9.98.0.4% H.sub.2O. Found %
C72.49; H6.31; N11.63; O9.57.0.4% H.sub.2O.
Example 7
[0269] 26
[0270] The procedure described in Example 7 is repeated except that
the compound of formula (101) is replaced by the equivalent amount
of the compound of formula (107) and 2-ethylhexanoyl chloride is
replaced by the equivalent amount of stearoyl chloride. After
working up, the compound of formula (108) is obtained in a yield of
98% of theory and has melting point of 222-224.degree. C.
[0271] Elemental analysis of the compound having the formula (107)
and having the empirical formula C.sub.39H.sub.50N.sub.4O.sub.3
gives:
[0272] Req.% C75.21; H8.09; N9.00; O7.71. Found % C75.14; H8.07;
N9.02; O7.86.
Example 8
[0273] 27
[0274] The procedure described in Example 7 is repeated except that
2-ethylhexanoyl chloride is replaced by the equivalent amount of
4-methoxybenzoyl chloride. After working up, the compound of
formula (109) is obtained in a yield of 25% of theory and has
melting point of 285-286.degree. C.
[0275] Elemental analysis of the compound having the formula (109)
and having the empirical formula C.sub.30H.sub.24N.sub.4O.sub.4
gives:
[0276] Req.% C71.42; H4.79; N11.10; O12.68. Found % C71.25; H4.80;
N11.20; O12.75.
Example 9
[0277] 28
[0278] The procedure described in Example 7 is repeated except that
2-ethylhexanoyl chloride is replaced by the equivalent amount of
dodecanoyl chloride. After working up, the compound of formula
(110) is obtained in a yield of 92% of theory and has melting point
of 182-183.degree. C. The UV spectra reading
[.lambda..sub.max(nm)/.epsilon.- (L/mol.cm)] is 320/55035, as
determined in CHCl.sub.3 at 25.degree. C.
[0279] Elemental analysis of the compound having the formula (110)
and having the empirical formula C.sub.34H.sub.40N.sub.4O.sub.3
gives:
[0280] Req.% C73.88; H7.29; N10.14; O8.68. Found % C73.75; H7.23;
N10.09; O8.92.
Example 10
[0281] 29
[0282] The procedure described in Example 7 is repeated except that
the compound of formula (101) is replaced by the equivalent amount
of the compound of formula (102) and that 2-ethylhexanoyl chloride
is replaced by the equivalent amount of oleic acid chloride. After
working up, the compound of formula (111) is obtained in a yield of
30% of theory and has melting point of 172-173.degree. C. The UV
spectra readings [.lambda..sub.max(nm)/.epsilon.(L/mol.cm)] are
279/38515 and 320/35055, as determined in CHCl.sub.3 at 25.degree.
C.
[0283] Elemental analysis of the compound having the formula (111)
and having the empirical formula C.sub.39H.sub.48N.sub.4O.sub.2
gives:
[0284] Req.% C77.45; H8.00; N9.26; O5.29. Found % C77.14; H7.75;
N9.42; O5.69.
Example 11
[0285] 30
[0286] The procedure described in Example 11 is repeated except
that oleic acid chloride is replaced by the equivalent amount of
dodecanoyl chloride. After working up, the compound of formula
(112) is obtained in a yield of 63% of theory and has melting point
of 222-223.degree. C. The UV spectra readings
[.lambda..sub.max(nm)/.epsilon.(L/mol.cm)] are 279137865 and
320134635, as determined in CHCl.sub.1 at 25.degree. C.
[0287] Elemental analysis of the compound having the formula (112)
and having the empirical formula C.sub.33H.sub.38N.sub.4O.sub.2
gives:
[0288] Req.% C75.83, H7.33; N10.72; O6.12. Found % C75.7; H7.3;
N10.7; O6.3.
Example 12
[0289] 31
[0290] The procedure described in Example 11 is repeated except
that oleic acid chloride is replaced by the equivalent amount of
acetyl chloride. After working up, the compound of formula (113) is
obtained in a yield of 93% of theory and has melting point of
317-318.degree. C. The UV spectra readings
[.lambda..sub.max(nm)/.epsilon.(L/mol.cm)] are 279/37442 and
318/33136, as determined in CHCl.sub.3 at 25.degree. C.
[0291] Elemental analysis of the compound having the formula (113)
and having the empirical formula C.sub.23H.sub.18N.sub.4O.sub.2
gives:
[0292] Req.% C72.24; H4.74; N14.65; O8.37. Found % C72.0; H4.9;
N14.7; O8.4.
Example 13
[0293] 32
[0294] The procedure described in Example 7 is repeated except that
2-ethylhexanoyl chloride is replaced by the equivalent amount of
acetyl chloride. After working up, the compound of formula (114) is
obtained in a yield of 99% of theory and has melting point above
300.degree. C. The UV spectra reading
[.lambda..sub.max(nm)/.epsilon.(L/mol.cm)] is 321/54075, as
determined in CHCl.sub.3 at 25.degree. C.
[0295] Elemental analysis of the compound having the formula (114)
and having the empirical formula C.sub.24H.sub.20N.sub.4O.sub.3
gives:
[0296] Req.% C69.89; H4.89; N13.58; O11.64. Found % C69.54; H4.86;
N13.52; O12.08.
Example 14
[0297] 33
[0298] The procedure described in Example 7 is repeated except that
2ethylhexanoyl chloride is replaced by the equivalent amount of
stearoyl chloride. After working up, the compound of formula (115)
is obtained in a yield of 97% of theory and has melting point of
172-173.degree. C.
[0299] Elemental analysis of the compound having the formula (115)
and having the empirical formula C.sub.40H.sub.52N.sub.4O.sub.3
gives:
[0300] Req.% C75.44, H8.23; N8.80; O7.54. Found % C75.29; H8.04;
N8.90; O7.77. 34
[0301] The procedure described in Example 7 is repeated except that
2-ethylhexanoyl chloride is replaced by the equivalent amount of
3,6,9-trioxadecanoyl chloride. After working up, the compound of
formula (116) is obtained in a yield of 65% of theory and has
melting point of 125-126.degree. C.
[0302] Elemental analysis of the compound having the formula (116)
and having the empirical formula C.sub.29H.sub.30N.sub.4O.sub.6
gives:
[0303] Req.% C65.65; H5.70; N10.56; O18.09. Found % C65.40; H5.76;
N10.39; O18.45. 35
[0304] A) 4.4 g of salicylamide in 25 mls of xyene (isomeric
mixture) are stirred with 12.2 g of 2-nitrobenzoyl chloride for 6
hours at 100.degree. C., until the development of HCl had largely
subsided. After cooling, a precipitate forms. The precipitate is
separated by suction, washed with xylene and dried to give 10.3 g
of colourless crystals. The colourless crystals are then reacted
with benzamidine, in methanol at 70.degree. C., to give the
compound (117A) as light yellow crystals of m.pt. 181-183.degree.
C., in a)yield of 80%.
[0305] Elemental analysis of the compound having the formula (117A)
and having the empirical formula C.sub.21H.sub.14N.sub.4O.sub.3
gives:
[0306] Req.% C67.1; H3.81; N15.12. Found % C67.41; H3.81; N15.10.
36
[0307] B) 6.4 g of compound (117A), obtained as described in part
A), are hydrogenated in dimethylacetamide using Raney-nickel
catalyst. The hydrogenation is conducted at 25.degree. C. at normal
pressure over 10 hours. After the catalyst is filtered off, a
orange solution remains. Compound (117) is precipitated from the
solution by the addition of water. Compound (117) is obtained in an
amount of 5.87 g (99% theory) as yellow crystals of m.pt. 21
8-220.degree. C. The UV spectra readings
[.lambda..sub.max(nm)/.epsilon.(L/mol.cm)] are 278/45004 and
351/10164, as determined in CHCl.sub.3 at 25.degree. C.
[0308] Elemental analysis of the compound having the formula (117)
and having the empirical formula C.sub.21H.sub.16N.sub.4O
gives:
[0309] Req.% C74.1; H4.74; N16.46. Found % C74.11; H4.76; N16.45.
37
[0310] A solution of 2.28 g of compound (117), obtained as
described in Example 17, in dimethylacetamide is reacted with 0.6 g
of acetyl chloride at 25.degree. C. and then stirred for 1 hour at
100.degree. C., whereupon a thickly flocculated product is
precipitated. After filtration with suction and washing with
dimethylacetamide, methanol and petrol, 2.25 g (88%) of the
compound of formula (118) are obtained having melting point of
201-203.degree. C. The UV spectra readings
[.lambda..sub.max(nm)/.epsi- lon.(L/mol.cm)] are 283/48316 and
354/15277, as determined in CHCl.sub.3 at 25.degree. C.
[0311] Elemental analysis of the compound having the formula (118)
and having the empirical formula C.sub.23H.sub.18N.sub.4O.sub.2
gives:
[0312] Req.% C72.24, H4.74; N14.65. Found % C72.60; H4.75; N14.70.
38
[0313] In an analogous procedure to that described in Example 18, a
solution of 2.28 g of the compound (117), obtained as described in
Example 17, in dimethylacetamide is reacted with 1.59 g of ethyl
chloroformate. After filtration with suction and drying, 1.95 g
(69.9%) of the compound of formula (119) are obtained having
melting point of 193-195.degree. C. The UV spectra readings
[.lambda..sub.max(nm)/.epsilon- .(L/mol.cm)] are 283150208 and
355115368, as determined in CHCl.sub.3 at 25.degree. C.
[0314] Elemental analysis of the compound having the formula (119)
and having the empirical formula C.sub.24H.sub.20N.sub.4O.sub.3
gives:
[0315] Req.% C69.89; H4.88; N13.58. Found % C70.12; H4.91; N13.73.
39
[0316] In an analogous procedure to that described in Example 13,
12.9 g of the compound of formula (102), obtained as described in
Example 2, are reacted with ethyl chloroformate. After filtration
with suction, washing with carbon tetrachloride and alcohol, and
then drying, 14.49 g (93%) of the compound of formula (120) are
obtained having m.pt. 247-249.degree. C. The UV spectra readings
[.lambda..sub.max(nm)/.epsilon.(L/mol.cm)] are 279/37530 and
319/33765, as determined in CHCl.sub.3 at 25.degree. C.
[0317] Elemental analysis of the compound having the formula (120)
and having the empirical formula C.sub.24H.sub.20N.sub.4O.sub.3
gives:
[0318] Req.% C69.89; H4.88; N13.58. Found % C69.55; H4.88; N13.55.
40
[0319] 8.25 g of the compound of formula (120), obtained as
described in Example 20, are heated in 10 g of
3-(2-methoxyethoxy)propylamine for 2 hours at 150.degree. C. The
reaction mixture is initially clear, it becomes cloudy after 20
minutes and, after 1 hour, it is solid. After cooling, the excess
amine is removed by boiling the reaction mixture twice with
acetone, using 150 mls of acetone each time. There remains 7.75 g
(78%) of almost colourless crystals of the compound (121) having
m.pt. 232-234.degree. C. The UV spectra readings
[.lambda..sub.max(nm)/.e- psilon.(L/mol.cm)] are 276134409 and
342138834, as determined in CHCl.sub.3 at 25.degree. C.
[0320] Elemental analysis of the compound having the formula (121)
and having the empirical formula C.sub.28H.sub.29N.sub.5O.sub.4
gives:
[0321] Req.% C67.32; H5.85; N14.02. Found % C67.42; H5.87; N14.04.
41
[0322] 8 g of the compound of formula (102), obtained as described
in Example 2, are suspended in 80 mls of dimethylacetamide and
treated with 5.5 g of 2-ethylhexyl chloroformate and the mixture is
stirred for 1 hour at 35.degree. C. A clear solution results. The
compound (122) is isolated by precipitation in 200 mls of ethyl
alcohol. After filtration with suction and washing with ethyl
alcohol and petrol ether, there are obtained 10.6 g (90.8%) of
light yellow crystals of the compound (122) having m.pt.
172-174.degree. C.
[0323] Elemental analysis of the compound having the formula (122)
and having the empirical formula C.sub.30H.sub.32N.sub.4O.sub.4
gives:
[0324] Req.% C72.56; H6.49; N11.28. Found % C72.55; H6.44; N11.61.
42
[0325] The procedure described in Example 7 is repeated except that
2-ethylhexanoyl chloride is replaced by the equivalent amount of
hexadecanoyl chloride. After working up, the compound of formula
(123) is obtained in a yield of 94.5% of theory and has melting
point of 165-167.degree. C.
[0326] Elemental analysis of the compound having the formula (123)
and having the empirical formula C.sub.38H.sub.48N.sub.4O.sub.3
gives:
[0327] Req.% C75.00; H7.95; N9.2; O7.88. Found % C75.00; H7.92;
N9.1; O7.89.
EXAMPLE 24
[0328] 43
[0329] The procedure described in Example 16 is repeated except
that the starting material is the compound of formula (102) instead
of the compound of formula (101). After working up, the compound of
formula (124) is obtained and has melting point of 90-91.degree.
C.
[0330] Elemental analysis of the compound having the formula (124)
and having the empirical formula C.sub.28H.sub.28N.sub.4O.sub.5
gives:
[0331] Req.% C67.19; H5.56; N11.19. Found% C66.80; H5.64;
N11.14.
EXAMPLE 25
[0332] 44
[0333] The procedure described in Example 16 is repeated except
that the starting material is the compound of formula (102) instead
of the compound of formula (101) and this is reacted with
methoxyacetyl chloride. After working up, the compound of formula
(125) is obtained in a yield of 89% of theory and has melting point
of 213-215.degree. C.
[0334] Elemental analysis of the compound having the formula (125)
and having the empirical formula C.sub.24H.sub.20N.sub.4O.sub.3
gives:
[0335] Req.% C69.89; H4.89; N13.58. Found % C69.96; H4.83;
N13.30.
EXAMPLE 26
[0336] 45
[0337] The procedure described in Example 24 is repeated except
that the starting material is the compound of formula (101) instead
of the compound of formula (102) and this is reacted with
methoxyacetyl chloride. After working up, the compound of formula
(126) is obtained in a yield of 89% of theory and has melting point
of 195-196.degree. C.
[0338] Elemental analysis of the compound having the formula (126)
and having the empirical formula C.sub.25H.sub.22N.sub.4O.sub.4
gives:
[0339] Req.% C67.86; H5.01; N12.66. Found % C67.33; H4.96;
N12.58.
EXAMPLES 27 to 32
[0340] Determination of Stability to UV Light
[0341] 100 mg of each test compound is dissolved in 100 mls of
chloroform to give a 1000 ppm stock solution. 10 ppm test solutions
are prepared by diluting the stock solution twice in the ratio 1/10
with chloroform. Molecular oxygen is removed from the test solution
before the irradiation by rinsing for 30 minutes with argon.
[0342] 200 mls of the test solution so prepared are placed in a UV
irradiation apparatus (DEMA 13/2 Fa. Hans Mangels) fitted with a
filter system and are irradiated with a UV lamp (HPK-125,
Phillips).
[0343] The test samples (3 mls each) are withdrawn through a fine
PET tube into a 5 ml one-way syringe and subjected directly to UV
spectroscopy. A Shimadzu UV-2100 spectometer is used having a
recording range of 220-420 nm
[0344] The determination of photostability is ascertained from the
difference between the UV-absorption spectrum of the original
compound and that measured after 24 hours exposure to UV
irradiation. The measurements are conducted at the wavelength of
the absorption maximum, if this lies in the wavelength range
300-400 nm, which is the relevant range for UV stabilisation. If
there is no maximum in this range, the absorption difference at 300
nm is measured.
[0345] The results are set out in the following Table.
1TABLE Example Compound .lambda. .epsilon.(before) .epsilon.(after)
.LAMBDA. % Loss 27 101 337 1.20 0.55 0.65 54 28 102 345 1.14 0.33
0.81 71 29 103 334 1.35 0.88 0.47 35 30 110 322 1.02 0.88 0.14 14
31 112 320 0.67 0.58 0.09 13 32 113 318 0.88 0.65 0.23 26
[0346] Compounds with poor photostability suffer complete erosion
of absorption after exposure for only a few minutes under these
test conditions. The results in the Table demonstrate, therefore,
the excellent stability of the compounds of the invention when
exposed to UV radiation for 24 hours.
EXAMPLE 33
[0347] Determination of High-temperature Lightfastness of Dyed
Polyester
[0348] A) 5 g of the compound of formula (113) are milled with 2.5
g of a dispersing agent (the condensation product of naphthalene
sulfonic acid and formaldehyde) dissolved in 15 mls of water. The
milling is conducted in the presence of 25 g of quartz spheres
(diameter 1 mm) using a stirrer rotating at 1600 rpm. The milling
is continued until the particle size is below 2 microns. The
dispersion is separated from the quartz spheres using a fine-mesh
screen and the dispersion is adjusted to a content of active
substance of 5.5% by the addition of water.
[0349] B) A 10 g sample of a polyester tricot is dyed in a
high-temperature dyeing apparatus, using a liquor ratio of 1:10.
The aqueous dye liquor used contains 2 g/l ammonium sulfate; 0.5
g/l of a dyeing auxiliary (Univadin.RTM. 3-flex); 0.5 wt. %, based
on the polyester tricot, of the formulation according to step A)
above; and 0.83 wt. %, based on the polyester tricot, of a dyestuff
mixture containing:
[0350] 33.7 wt. % of C.l.Disperse Yellow 42,
[0351] 15.7 wt. % of C.l.Disperse Red 86,
[0352] 19.3 wt. % of C.l.Disperse Blue 60 and
[0353] 31.3 wt. % of C.l.Disperse Violet 57.
[0354] The dye liquor is adjusted to pH 5 with acetic acid,
homogenised and placed in a pressure bomb with the tricot The
dyeing is started at 70.degree. C. and then the temperature is
raised to 130.degree. C. over 30 minutes. After a dyeing time of 60
minutes at this temperature, cooling to 75.degree. C. is effected,
the dyed goods are rinsed hot and cold and they are reductively
cleaned at 70.degree. C. with a liquor containing 3 ml/l of 30%
aqueous sodium hydroxide and 2 g/l of sodium dithionite. After
rinsing and drying, a grey-dyed polyester tricot is obtained which
has a very good high temperature lightfastness.
[0355] When the dyeing is conducted using a dye liquor which does
not contain the formulation according to step A) above, a dyeing is
obtained which has a significantly reduced high temperature
lightfastness.
EXAMPLES 34 to 38
[0356] Stabilisation of a 2-layer Metallic Lacquer
[0357] Various test light stabilisers are dissolved in 20-30 g of
an aromatic hydrocarbon mixture (boiling range 182-203.degree. C.)
and tested in clear lacquer having the following composition:
2 acrylate resin (65% solution in xylene/butanol 26:9) 27.51
acrylate resin (75% solution in an aromatic 23.34 hydrocarbon
mixture (boiling range 161-178.degree. C.) melamine resin (55%
solution in isobutanol) 27.29 butyl acetate/butanol (37:8) 4.33
isobutanol 4.87 aromatic hydrocarbon mixture (boiling range
182-203.degree. C.) 2.72 aliphatic hydrocarbon mixture (boiling
range 145-200.degree. C.) 8.74 flow aid (1% in aromatic hydrocarbon
mixture (boiling range 1.20 182-203.degree. C.) 100.00 g
[0358] 1.5% by weight of each of the test stabilisers is added to
separate samples of the clear lacquer. A further set of test
lacquers are prepared which contain, in addition to the test
stabilisers of the present invention, 1% by weight of the known
light stabiliser compound having the formula: 46
[0359] Comparative tests are conducted using clear lacquer samples
containing no light stabiliser compounds.
[0360] The various clear lacquer samples are diluted with an
aromatic hydrocarbon mixture (boiling range 161-178.degree. C.) to
obtain a consistency suitable for spraying. The diluted samples are
then sprayed on to a prepared aluminium sheet (Uniprime Epoxy,
silver metallic base lacquer and stoved at 130.degree. C. for 30
minutes. A dry film thickness of 40-50 .mu.m of each clear lacquer
is obtained.
[0361] Each test sample is subjected to weathering using a
UVCON.RTM. weathering apparatus (UVB-313 lamps) using a cycle
consisting of an 8 hour irradiation at 70.degree. C. and a 4 hour
condensation at 50.degree. C. The surface gloss of each weathered
sample is measured (200 gloss, DIN 67530) initially, and after 400,
800,1200 and 1600 hours, respectively.
[0362] The results obtained using the test light stabilisers of the
present invention alone are set out in the following Table:
3 20.degree. gloss/exposure hours Example Test Cpd. 0 400 800 1200
1600 -- none 92 90 34 15 -- 34 cpd. (123) 90 84 86 85 74 35 cpd.
(116) 92 95 94 94 94 36 cpd. (115) 89 83 82 81 81 37 cpd. (110) 85
67 70 74 66 38 cpd. (104) 92 94 93 92 92
[0363] The results obtained using the test light stabilisers of the
present invention together with the known light stabiliser are set
out in the following Table:
4 20.degree. gloss/exposure hours Example Test Cpd. 0 400 800 1200
1600 -- none 92 86 49 14 -- 34 cpd. (123) 91 88 87 87 87 35 cpd.
(116) 93 94 95 96 96 36 cpd. (115) 90 87 85 82 85 37 cpd. (110) 85
80 74 72 72 38 cpd. (104) 93 94 92 94 94
[0364] These results clearly demonstrate the improved resistance to
weathering (as shown by superior gloss retention) of the stabilised
compositions of the invention, relative to the unstabilised
compositions.
EXAMPLE 39
[0365] Preparation of a Sun Protection Cream
[0366] The compound of formula (113) is ground in water containing
quartz sand and 8% of phospholipid (Phospholipone 80), as
auxiliary, to a mean particle size of 250 nm. The nanopigment
suspension so obtained is then incorporated into the following
composition.
5 Phase A dimethicone 2% isopropyl myristate 9% stearyl alcohol 10%
stearic acid 4% octyl methoxycinnamate 3.5% Phase B triethanolamine
1.2% Carbomer 934 (1%) 5.0% compound (113) as 50% suspension 9.6%
(4.85% active) water 55.7%
[0367] Phase A is separately very carefully homogenised and, as
with Phase B. is then separately heated to 75-80.degree. C. Phase B
is then added, with vigorous stirring, to Phase A. Whilst stirring,
the mixture is allowed to cool.
[0368] Using the SPF analyser (SPF 290 ex Optometrix) the light
protection factor of the sun protection cream so obtained is found
to be 22. The permeability of the sun protection cream so obtained
to the UVA component at 360 nm is zero.
EXAMPLE 40
[0369] Preparation of a Sun Protection Emulsion
[0370] The compound of formula (102) is ground in water containing
"zirconium sand" and 7% of Plantaren 2000 to a mean particle size
of 180 nm. The nanopigment suspension so obtained is then
incorporated into the following composition.
6 Phase A Ceteareth-6 and stearyl alcohol 2% Ceteareth-25 2%
cetearyl alcohol 5% caprylic/capric triglyceride 5% cetearyl
octanoate 10% vaseline 5% Phase B propylene glycol 3% Carbopol 934
(1%) 0.2% compound (113) as 50% suspension 10% (5% active) water
57.53% Phase C triethanolamine 0.27%
[0371] Phases A and B are separately heated to 75-80.degree. C.
Phase B is then added to Phase A, with vigorous homogenisation,
followed by Phase C and the whole is intensively
re-homogenised.
[0372] Using the SPF analyser (SPF 290 ex Optometrix) the light
protection factor of the sun protection cream so obtained is found
to be 11. The permeability of the sun protection oil-in-water
emulsion so obtained to the UVA component at 360 nm is zero.
EXAMPLES 41 and 42
[0373] 10 g of polycarbonate powder (Lexan 115) are dissolved, with
stirring at 25.degree. C., in 50 g of methylene chloride. Several
hours stirring are required. Then 0.2 g of the test UV absorber is
added (2% on the polycarbonate). From the resulting solution there
is cast a film having a thickness of 20 microns.
[0374] The respective films are exposed in an Atlas Weatherometer
Cl 65 at a black table temperature of 63.degree. C. and a relative
humidity of 60%. At regular intervals, the discolouration of the
samples is examined by measuring the Yellowness Index (YI, DIN 6167
method).
[0375] In the following Table, there are set out the respective
exposure times (in hours) required for the test films to reach a
Yellowness Index of 5 or 7.
7TABLE Exposure time (hours) to reach: Example UV absorber YI = 5
YI = 7 -- none 900 1000 41 compound (125) 2150 3350 42 compound
(126) 1780 3100
[0376] Polycarbonate is especially sensitive to light and tends to
yellow rapidly. Accordingly, the results in the Table demonstrate
that the test compounds used in Examples 41 and 42 are very
valuable UV absorbers for polycarbonate.
EXAMPLES 43 and 44
[0377] To 100 parts of polyoxymethylene copolymer (unstabilised)
there are added 0.1 part of calcium stearate, 0.1 part of melamine
and 0.3 part of an antioxidant (Irganox 245). To this mixture there
are then added 0.3 part of a hindered amine light stabiliser
(Tinuvin 622) and 0.3 part of the test UV absorber. The powder
mixture is mixed well at 25.degree. C. using a "Henkel" mixer. The
powder mixture is then extruded to granulate in a double-screw
extruder operating at 150 rpm using a temperature profile of
45/180/190.degree. C. The granulate is then converted into plates
(2 mm) in an injection moulding device.
[0378] The respective plates are exposed in an Atlas Weatherometer
Cl 65 at a black table temperature of 55.degree. C. using the cycle
of 102 minutes dry and 18 minutes wet. At regular intervals, the
gloss of the respective plates is determined using a gloss
measuring device (Micro Gloss, Byk Gardner) with the adjustment of
601 to the light measurement. The results obtained are set out in
the following Table.
8 Gloss after 0, 250, 500, 750, 1000 or 1250 hours Example UV
Absorber 0 250 500 750 1000 1250 -- none 78 76 73 73* 72* 72* 43
Cpd. (116) 79 77 77 78 78 78 44 Cpd. (124) 76 75 75 75 75 76
[0379] After 750, 1000 and 1250 hours, the control sample developed
cracks.
[0380] The results demonstrate that the test compounds of Examples
43 and 44 are valuable UV absorbers for use in polyoxymethylene
copolymer.
* * * * *