U.S. patent application number 10/945514 was filed with the patent office on 2005-03-03 for stabilizer mixtures.
Invention is credited to Gugumus, Francois.
Application Number | 20050049336 10/945514 |
Document ID | / |
Family ID | 8174807 |
Filed Date | 2005-03-03 |
United States Patent
Application |
20050049336 |
Kind Code |
A1 |
Gugumus, Francois |
March 3, 2005 |
Stabilizer mixtures
Abstract
A stabilizer mixture containing (I) two different sterically
hindered amine compounds, and (II) at least one compound selected
from the group consisting of an organic salt of Zn, an inorganic
salt of Zn, Zn oxide, Zn hydroxide, an organic salt of Mg, an
inorganic salt of Mg, Mg oxide and Mg hydroxide.
Inventors: |
Gugumus, Francois;
(Alischwil, CH) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION
PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
8174807 |
Appl. No.: |
10/945514 |
Filed: |
September 20, 2004 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10945514 |
Sep 20, 2004 |
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09899438 |
Jul 5, 2001 |
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6828364 |
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Current U.S.
Class: |
524/90 |
Current CPC
Class: |
C08K 5/098 20130101;
C08K 5/3435 20130101; C08K 5/353 20130101; C08L 23/02 20130101;
C08K 5/005 20130101; C08K 5/34926 20130101; C08K 5/005
20130101 |
Class at
Publication: |
524/090 |
International
Class: |
C08K 005/48 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 14, 2000 |
EP |
00810621.3 |
Claims
1. A stabilizer mixture containing (I) two different sterically
hindered amine compounds, and (II) at least one compound selected
from the group consisting of an organic salt of Zn, an inorganic
salt of Zn, Zn oxide, Zn hydroxide, an organic salt of Mg, an
inorganic salt of Mg, Mg oxide and Mg hydroxide; with the proviso
that component (I) is different from the combination of the
compounds (B-8-a) and (B-8-b) 89 wherein n.sub.2 and n.sub.2* are a
number from 2 to 50; and with the proviso that, when component (I)
is the combination of the compounds (B-1-a-1) and (B-7-a);
90wherein b.sub.1 is a number from 2 to 50, 91wherein n.sub.1 is a
number from 2 to 50; and, at the same time, component (II) is a Zn
carboxylate; the stabilizer mixture additionally contains as a
further component (X-1) a pigment or (X-2) an UV absorber or (X-3)
a pigment and an UV absorber.
2. A stabilizer mixture according to claim 1 wherein the two
different sterically hindered amine compounds of component (I) are
selected from the group consisting of (.alpha.-1) a compound of the
formula (A-1) 92in which E.sub.1 is hydrogen, C.sub.1-C.sub.8alkyl,
O.sup.-, --OH, --CH.sub.2CN, C.sub.1-C.sub.18alkoxy,
C.sub.5-C.sub.12cycloalkoxy, C.sub.3-C.sub.6alkenyl,
C.sub.7-C.sub.9phenylalkyl unsubstituted or substituted on the
phenyl by 1, 2 or 3 C.sub.1-C.sub.4alkyl; or C.sub.1-C.sub.8acyl,
m.sub.1 is 1, 2 or 4, if m.sub.1 is 1, E.sub.2 is
C.sub.1-C.sub.25alkyl, if m.sub.1 is 2, E.sub.2 is
C.sub.1-C.sub.14alkylene or a group of the formula (a-I) 93wherein
E.sub.3 is C.sub.1-C.sub.10alkyl or C.sub.2-C.sub.10alkenyl,
E.sub.4 is C.sub.1-C.sub.10alkylene, and E.sub.5 and E.sub.6
independently of one another are C.sub.1-C.sub.4alkyl, cyclohexyl
or methylcyclohexyl, and if m.sub.1 is 4, E.sub.2 is
C.sub.4-C.sub.10alkanetetrayl; (.alpha.-2) a compound of the
formula (A-2) 94in which two of the radicals E.sub.7 are
--COO--(C.sub.1-C.sub.20alkyl), and two of the radicals E.sub.7 are
a group of the formula (a-II) 95with E.sub.8 having one of the
meanings of E.sub.1; (.alpha.-3) a compound of the formula (A-3)
96in which E.sub.9 and E.sub.10 together form
C.sub.2-C.sub.14alkylene, E.sub.11 is hydrogen or a group
-Z.sub.1-COO-Z.sub.2, Z.sub.1 is C.sub.2-C.sub.14alkylene, and
Z.sub.2 is C.sub.1-C.sub.24alkyl, and E.sub.12 has one of the
meanings of E.sub.1; (.alpha.-4) a compound of the formula (A-4)
97wherein the radicals E.sub.13 independently of one another have
one of the meanings of E.sub.1, the radicals E.sub.14 independently
of one another are hydrogen or C.sub.1-C.sub.12alkyl, and E.sub.15
is C.sub.1-C.sub.10alkylene or C.sub.3-C.sub.10alkylidene;
(.alpha.-5) a compound of the formula (A-5) 98wherein the radicals
E.sub.16 independently of one another have one of the meanings of
E.sub.1; (.alpha.-6) a compound of the formula (A-6) 99in which
E.sub.17 is C.sub.1-C.sub.24alkyl, and E.sub.18 has one of the
meanings of E.sub.1; (.alpha.-7) a compound of the formula (A-7)
100in which E.sub.19, E.sub.20 and E.sub.21 independently of one
another are a group of the formula (a-III) 101wherein E.sub.22 has
one of the meanings of E.sub.1; (.alpha.-8) a compound of the
formula (A-8) 102wherein the radicals E.sub.23 independently of one
another have one of the meanings of E.sub.1, and E.sub.24 is
hydrogen, C.sub.1-C.sub.12alkyl or C.sub.1-C.sub.12alkoxy;
(.alpha.-9) a compound of the formula (A-9) 103wherein m.sub.2 is
1, 2 or 3, E.sub.25 has one of the meanings of E.sub.1, and when
m.sub.2 is 1, E.sub.26 is a group 104when m.sub.2 is 2, E.sub.26 is
C.sub.2-C.sub.22alkylene, and when m.sub.2 is 3, E.sub.26 is a
group of the formula (a-IV) 105wherein the radicals E.sub.27
independently of one another are C.sub.2-C.sub.12alkylene, and the
radicals E.sub.28 independently of one another are
C.sub.1-C.sub.12alkyl or C.sub.5-C.sub.12cycloalkyl; (.alpha.-10) a
compound of the formula (A-10) 106wherein the radicals E.sub.29
independently of one another have one of the meanings of E.sub.1,
and E.sub.30 is C.sub.2-C.sub.22alkylene,
C.sub.5-C.sub.7cycloalkylene,
C.sub.1-C.sub.4alkylenedi(C.sub.5-C.sub.7cycloalkylene), phenylene
or phenylenedi(C.sub.1-C.sub.4alkylene); (.beta.-1) a compound of
the formula (B-1) 107in which R.sub.1, R.sub.3, R.sub.4 and R.sub.5
independently of one another are hydrogen, Cl-C.sub.12alkyl,
C.sub.5-C.sub.12cycloalkyl, C.sub.1-C.sub.4-alkyl-substituted
C.sub.5-C.sub.12cycloalkyl, phenyl, phenyl which is substituted by
--OH and/or C.sub.1-C.sub.10alkyl; C.sub.7-C.sub.9phenylalkyl,
C.sub.7-C.sub.9phenylalkyl which is substituted on the phenyl
radical by --OH and/or C.sub.1-C.sub.10alkyl; or a group of the
formula (b-I) 108R.sub.2 is C.sub.2-C.sub.18alkylene,
C.sub.5-C.sub.7cycloalkylene or
C.sub.1-C.sub.4alkylenedi(B.sub.5-C.sub.7cycloalkylene), or the
radicals R.sub.1, R.sub.2 and R.sub.3, together with the nitrogen
atoms to which they are bonded, perform a 5- to 10-membered
heterocyclic ring, or R.sub.4 and R.sub.5, together with the
nitrogen atom to which they are bonded, form a 5- to 10-membered
heterocyclic ring, R.sub.6 is hydrogen, C.sub.1-C.sub.8alkyl,
O.sup.-, --OH, --CH.sub.2CN, C.sub.1-C.sub.18alkoxy,
C.sub.5-C.sub.12cycloalkoxy, C.sub.3-C.sub.6alkenyl,
C.sub.7-C.sub.9phenylalkyl unsubstituted or substituted on the
phenyl by 1, 2 or 3 C.sub.1-C.sub.4alkyl; or C.sub.1-C.sub.8acyl,
and b.sub.1 is a number from 2 to 50, with the proviso that at
least one of the radicals R.sub.1, R.sub.3, R.sub.4 and R.sub.5 is
a group of the formula (b-I); (.beta.-2) a compound of the formula
(B-2) 109wherein R.sub.7 and R.sub.11 independently of one another
are hydrogen or C.sub.1-C.sub.12alkyl, R.sub.8, R.sub.9 and
R.sub.10 independently of one another are C.sub.2-C.sub.10alkylene,
and X.sub.1, X.sub.2, X.sub.3, X.sub.4, X.sub.5, X.sub.6, X.sub.7
and X.sub.8 independently of one another are a group of (b-II),
110in which R.sub.12 is hydrogen, C.sub.1-C.sub.12alkyl,
C.sub.5-C.sub.12cycloalkyl, C.sub.1-C.sub.4alkyl-substituted
C.sub.5-C.sub.12cycloalkyl, phenyl, --OH-- and/or
C.sub.1-C.sub.10alkyl-substituted phenyl,
C.sub.7-C.sub.9phenylalkyl, C.sub.7-C.sub.9phenylalkyl which is
substituted on the phenyl radical by --OH and/or
C.sub.1-C.sub.10alkyl; or a group of the formula (b-I) as defined
above, and R.sub.13 has one of the meanings of R.sub.6; (.beta.-3)
a compound of the formula (B-3) 111in which R.sub.14 is
C.sub.1-C.sub.10alkyl, C.sub.5-C.sub.12cycloalkyl- ,
C.sub.1-C.sub.4alkyl-substituted C.sub.5-C.sub.12cycloalkyl, phenyl
or C.sub.1-C.sub.10alkyl-substituted phenyl, R.sub.15 is
C.sub.3-C.sub.10alkylene, R.sub.16 has one of the meanings of
R.sub.6, and b.sub.2 is a number from 2 to 50; (.beta.-4) a
compound of the formula (B-4) 112in which R.sub.17 and R.sub.21
independently of one another are a direct bond or a
--N(X.sub.9)-CO-X.sub.10-CO--N(X.sub.11)- group, where X.sub.9 and
X.sub.11 independently of one another are hydrogen,
C.sub.1-C.sub.8alkyl, C.sub.5-C.sub.12cycloalkyl, phenyl,
C.sub.7-C.sub.9phenylalkyl or a group of the formula (b-I),
X.sub.10 is a direct bond or C.sub.1-C.sub.4alkylene, R.sub.18 has
one of the meanings of R.sub.6, R.sub.19, R.sub.20, R.sub.23 and
R.sub.24 independently of one another are hydrogen,
C.sub.1-C.sub.30alkyl, C.sub.5-C.sub.12cycloalk- yl or phenyl,
R.sub.22 is hydrogen, C.sub.1-C.sub.30alkyl,
C.sub.5-C.sub.12cycloalkyl, phenyl, C.sub.7-C.sub.9phenylalkyl or a
group of the formula (b-I), and b.sub.3 is a number from 1 to 50;
(.beta.-5) a compound of the formula (B-5) 113in which R.sub.25,
R.sub.26, R.sub.27, R.sub.28 and R.sub.29 independently of one
another are a direct bond or C.sub.1-C.sub.10alkylene, R.sub.30 has
one of the meanings of R.sub.6, and b.sub.4 is a number from 1 to
50; (.beta.-6) a product (B-6) obtainable by reacting a product,
obtained by reaction of a polyamine of the formula (B-6-1) with
cyanuric chloride, with a compound of the formula (B-6-2) 114in
which b'.sub.5, b".sub.5 and b'".sub.5 independently of one another
are a number from 2 to 12, R.sub.31 is hydrogen,
C.sub.1-C.sub.12alkyl, C.sub.5-C.sub.12cycloalkyl, phenyl or
C.sub.7-C.sub.9phenylalkyl, and R.sub.32 has one of the meanings of
R.sub.6; (.beta.-7) a compound of the formula (B-7) 115wherein
A.sub.1 is hydrogen or C.sub.1-C.sub.4alkyl, A.sub.2 is a direct
bond or C.sub.1-C.sub.10alkylene, and n.sub.1 is a number from 2 to
50; (.beta.-8) at least one compound of the formulae (B-8-a) and
(B-8-b) 116wherein n.sub.2 and n.sub.2* are a number from 2 to 50;
(.beta.-9) a compound of the formula (B-9) 117wherein A.sub.3 and
A.sub.4 independently of one another are hydrogen or
C.sub.1-C.sub.8alkyl, or A.sub.3 and A.sub.4 together form a
C.sub.2-C.sub.14alkylene group, and the variables n.sub.3
independently of one another are a number from 1 to 50; and
(.beta.-10) a compound of the formula (B-10) 118wherein n.sub.4 is
a number from 2 to 50, A.sub.5 is hydrogen or C.sub.1-C.sub.4alkyl,
the radicals A.sub.6 and A.sub.7 independently of one another are
C.sub.1-C.sub.4alkyl or a group of the formula (b-I), with the
proviso that at least 50% of the radicals A.sub.7 are a group of
the formula (b-I) and with the proviso that the stablizer mixtures
containing both of the two different stericallly hindered amine
compounds selected from the group consisting of the classes
(.beta.-1), (.beta.-2), (.beta.-6), (.beta.-7) and (.beta.-8) are
excluded.
3. A stabilizer mixture according to claim 2, wherein the two
different sterically hindered amine compounds of component (I) are
selected from the group consisting of the classes (.alpha.-1),
(.alpha.-2), (.alpha.-3), (.alpha.-4), (.alpha.-5), (.alpha.-6),
(.alpha.-7), (.alpha.-8), (.alpha.-9) and (.alpha.-10).
4. A stabilizer mixture according to claim 2, wherein the two
different sterically hindered amine compounds of component (I) are
selected from the group consisting of the classes (.beta.-3),
(.beta.-4), (.beta.-5), (.beta.-9) and (.beta.-10).
5. A stabilizer mixture according to claim 2, wherein one of the
two different sterically hindered amine compounds of component (I)
is selected from the group consisting of the classes (.alpha.-1),
(.alpha.-2), (.alpha.-3), (.alpha.-4), (.alpha.-5), (.alpha.-6),
(.alpha.-7), (.alpha.-8), (.alpha.-9) and (.alpha.-10), and the
other of the two different sterically hindered amine compounds of
component (I) is selected from the group consisting of the classes
(.beta.-1), (.beta.-2), (.beta.-3), (.beta.-4), (.beta.-5),
(.beta.-6), (.beta.-7), (.beta.-8), (.beta.-9) and (.beta.-10).
6. A stabilizer mixture according to claim 2, wherein one of the
two different sterically hindered amine compounds of component (I)
is selected from the class (.beta.-1) with the proviso that the
other of the two different sterically hindered amine compounds
selected from the group consisting of the classes ((.beta.-1),
(.beta.-2), (.beta.-6), (.beta.-7), and (.beta.-8) is excluded.
7. A stabilizer mixture according to claim 2, wherein one of the
two different sterically hindered amine compounds of component (I)
is selected from the class (.beta.-1), and the other of the two
different sterically hindered amine compounds of component (I) is
selected from the class (.alpha.-1).
8. (cancelled).
9. A stabilizer mixture according to claim 2, wherein the two
different sterically hindered amine compounds of component (I) are
selected from different classes.
10. A stabilizer mixture according to claim 2, wherein m.sub.1 is
1, 2 or 4, if m.sub.1 is 1, E.sub.2 is C.sub.12-C.sub.20alkyl, if
m.sub.1 is 2, E.sub.2 is C.sub.2-C.sub.10alkylene or a group of the
formula (a-I) E.sub.3 is C.sub.1-C.sub.4alkyl, E.sub.4 is
C.sub.1-C.sub.6alkylene, and E.sub.5 and E.sub.6 independently of
one another are C.sub.1-C.sub.4alkyl, and if m.sub.1 is 4, E.sub.2
is C.sub.4-C.sub.8alkanetetrayl; two of the radicals E.sub.7 are
--COO--(C.sub.10-C.sub.15alkyl), and two of the radicals E.sub.7
are a group of the formula (a-II); E.sub.9 and E.sub.10 together
form C.sub.9-C.sub.13alkylene, E.sub.11 is hydrogen or a group
-Z.sub.1-COO-Z.sub.2, Z.sub.1 is C.sub.2-C.sub.6alkylene, and
Z.sub.2 is C.sub.10-C.sub.16alkyl; E.sub.14 is hydrogen, and
E.sub.15 is C.sub.2-C.sub.6alkylene or C.sub.3-C.sub.5alkylidene;
E.sub.17 is C.sub.10-C.sub.14alkyl; E.sub.24 is
C.sub.1-C.sub.4alkoxy; m.sub.2 is 1, 2 or 3, when m.sub.2 is 1,
E.sub.26 is a group 119when m.sub.2 is 2, E.sub.26 is
C.sub.2-C.sub.6alkylene, and when m.sub.2 is 3, E.sub.26 is a group
of the formula (a-IV) the radicals E.sub.27 independently of one
another are C.sub.2-C.sub.6alkylene, and the radicals E.sub.28
independently of one another are C.sub.1-C.sub.4alkyl or
C.sub.5-C.sub.8cycloalkyl; and E.sub.30 is C.sub.2-C.sub.8alkylene;
R.sub.1 and R.sub.3 independently of one another are a group of the
formula (b-I), R.sub.2 is C.sub.2-C.sub.8alkylene, R.sub.4 and
R.sub.5 independently of one another are hydrogen,
C.sub.1-C.sub.12alkyl, C.sub.5-C.sub.8cycloalkyl or a group of the
formula (b-I), or the radicals R.sub.4 and R.sub.5, together with
the nitrogen atom to which they are bonded, form a 5- to
10-membered heterocyclic ring, and b.sub.1 is a number from 2 to
25; R.sub.7 and R.sub.11 independently of one another are hydrogen
or C.sub.1-C.sub.4alkyl, R.sub.8, R.sub.9 and R.sub.10
independently of one another are C.sub.2-C.sub.4alkylene, and
X.sub.1, X.sub.2, X.sub.3, X.sub.4, X.sub.5, X.sub.6, X.sub.7 and
X.sub.8 independently of one another are a group of the formula
(b-II), R.sub.12 is hydrogen, C.sub.1-C.sub.4alkyl,
C.sub.5-C.sub.8cycloalkyl or a group of the formula (b-I); R.sub.14
is C.sub.1-C.sub.4alkyl, R.sub.15 is C.sub.3-C.sub.6alkylene, and
b.sub.2 is a number from 2 to 25; R.sub.17 and R.sub.21
independently of one another are a direct bond or a group
--N(X.sub.9)-CO-X.sub.10-CO--N(X.sub.11)-, X.sub.9 and X.sub.11
independently of one another are hydrogen or C.sub.1-C.sub.4alkyl,
X.sub.10 is a direct bond, R.sub.19 and R.sub.23 are
C.sub.1-C.sub.25alkyl or phenyl, R.sub.20 and R.sub.24 are hydrogen
or C.sub.1-C.sub.4alkyl, R.sub.22 is C.sub.1-C.sub.25alkyl or a
group of the formula (b-I), and b.sub.3 is a number from 1 to 25;
R.sub.25, R.sub.26, R.sub.27, R.sub.28 and R.sub.29 independently
of one another are a direct bond or C.sub.1-C.sub.4alkylene, and
b.sub.4 is a number from 1 to 25; b'.sub.5, b".sub.5 and b'".sub.5
independently of one another are a number from 2 to 4, and R.sub.31
is hydrogen, C.sub.1-C.sub.4alkyl, C.sub.5-C.sub.8cycloalkyl,
phenyl or benzyl; A.sub.1 is hydrogen or methyl, A.sub.2 is a
direct bond or C.sub.2-C.sub.6alkylene, and n.sub.1 is a number
from 2 to 25; n.sub.2 and n.sub.2* are a number from 2 to 25;
A.sub.3 and A.sub.4 independently of one another are hydrogen or
C.sub.1-C.sub.4alkyl, or A.sub.3 and A.sub.4 together form a
C.sub.9-C.sub.13alkylene group, and the variables n.sub.3
independently of one another are a number from 1 to 25; n.sub.4 is
a number from 2 to 25, A.sub.5 and A.sub.6 independently of one
another are C.sub.1-C.sub.4alkyl, and A.sub.7 is
C.sub.1-C.sub.4alkyl or a group of the formula (b-I) with the
proviso that at least 50% of the radicals A.sub.7 are a group of
the formula (b-I).
11. A stabilizer mixture according to claim 1, wherein the two
different sterically hindered amine compounds of component (I) are
selected from the group consisting of the compounds of the formulae
(A-1-a), (A-1-b), (A-1-c), (A-1-d), (A-2-a), (A-3-a), (A-3-b),
(A-4-a), (A-4-b), (A-5), (A-6-a), (A-7), (A-8-a), (A-9-a), (A-9-b),
(A-9-c), (A-10-a), (B-1-a), (B-1-b), (B-1-c), (B-1-d), (B-2-a),
(B-3-a), (B-4-a), (B-4-b) and (B-4-c), a product (B-6-a) and the
compounds of the formulae (B-7-a), (B-8-a), (B-8-b), (B-9-a) and
(B-10-a); 120wherein E.sub.1 is hydrogen, C.sub.1-C.sub.8alkyl,
O.sup.-, --OH, --CH.sub.2CN, C.sub.1-C.sub.18alkoxy,
C.sub.5-C.sub.12cycloalkoxy, C.sub.3-C.sub.6alkenyl,
C.sub.7-C.sub.9phenylalkyl unsubstituted or substituted on the
phenyl by 1, 2 or 3 C.sub.1-C.sub.4alkyl; or C.sub.1-C.sub.8acyl;
121in which two of the radicals E.sub.7 are --COO--C.sub.13H.sub.27
and two of the radicals E.sub.7 are 122 and E.sub.8 has one of the
meanings of E.sub.1; 123wherein E.sub.12 has one of the meanings of
E.sub.1; 124wherein E.sub.13 has one of the meanings of E.sub.1;
125wherein E.sub.16 has one of the meanings of E.sub.1; 126wherein
E.sub.18 has one of the meanings of E.sub.1; 127in which E.sub.19,
E.sub.20 and E.sub.21 independently of one another are a group of
the formula (a-III) 128wherein E.sub.22 has one of the meanings of
E.sub.1; 129wherein E.sub.23 has one of the meanings of E.sub.1;
130wherein E.sub.25 has one of the meanings of E.sub.1; 131wherein
E.sub.29 has one of the meanings of E.sub.1; 132wherein b.sub.1 is
a number from 2 to 20 and R.sub.6 is hydrogen,
C.sub.1-C.sub.8alkyl, O.sup.-, --OH, --CH.sub.2CN,
C.sub.1-C.sub.18alkoxy, C.sub.5-C.sub.12cycloalkoxy,
C.sub.3-C.sub.6alkenyl, C.sub.7-C.sub.9phenylalkyl unsubstituted or
substituted on the phenyl by 1, 2 or 3 C.sub.1-C.sub.4alkyl; or
C.sub.1-C.sub.8acyl; 133wherein R.sub.13 has one of the meanings of
R.sub.6, 134wherein b.sub.2 is a number from 2 to 20 and R.sub.16
has one of the meanings of R.sub.6; 135wherein b.sub.4 is a number
from 1 to 20 and R.sub.30 has one of the meanings of R.sub.6; a
product (B-6-a) obtainable by reacting a product, obtained by
reaction of a polyamine of the formula (B-6-1-a) with cyanuric
chloride, with a compound of the formula (B-6-2-a) 136in which
R.sub.32 has one of the meanings of R.sub.6; 137wherein n.sub.1 is
a number from 2 to 20; 138wherein n.sub.2 and n.sub.2* are a number
from 2 to 20; 139wherein the variables n.sub.3 independently of one
another are a number from 1 to 20; 140wherein n.sub.4 is a number
from 2 to 20, and at least 50% of the radicals A.sub.7 are a group
of the formula (b-I) 141wherein R.sub.6 is hydrogen,
C.sub.1-C.sub.8alkyl, O.sup.-, --OH, --CH.sub.2CN,
C.sub.1-C.sub.18alkoxy, C.sub.5-C.sub.12cycloalkoxy,
C.sub.3-C.sub.6alkenyl, C.sub.7-C.sub.9phenylalkyl unsubstituted or
substituted on the phenyl by 1, 2 or 3 C.sub.1-C.sub.4alkyl; or
C.sub.1-C.sub.8acyl, and the remaining radicals A.sub.7 are ethyl,
with the proviso that the stablizer mixtures containing both of the
two different stericallly hindered amine compounds selected from
the group consisting of B-1-a, B-1-b, B-1-c, B-1-d, B-2-a, a
product B-6-a defined as above, B-7-a, B-8-a and B-8-b are
excluded.
12. A stabilizer mixture according to claim 11 wherein the two
different sterically hindered amine compounds of component (I) are
a compound of the formula (A-1-b) wherein E.sub.1 is hydrogen, and
a compound of the formula (B-1-a) wherein R.sub.6 is hydrogen;
13. A stabilizer mixture according to claim 2 wherein E.sub.1,
E.sub.8, E.sub.12, E.sub.13, E.sub.16, E.sub.18, E.sub.22,
E.sub.23, E.sub.25, E.sub.29, R.sub.6, R.sub.13, R.sub.16,
R.sub.18, R.sub.30 and R.sub.32 are hydrogen, C.sub.1-C.sub.4alkyl,
C.sub.1-C.sub.10alkoxy, cyclohexyloxy, allyl, benzyl or acetyl.
14. A stabilizer mixture according to claim 11 wherein E.sub.1,
E.sub.8, E.sub.12, E.sub.13, E.sub.16, E.sub.18, E.sub.22,
E.sub.23, E.sub.25, E.sub.29, R.sub.6, R.sub.13, R.sub.16,
R.sub.18, R.sub.30 and R.sub.32 are hydrogen or methyl and E.sub.1
and R.sub.6 additionally are C.sub.1-C.sub.8alkoxy.
15. A stabilizer mixture according to claim 1, wherein the compound
of component (II) is selected from the group consisting of Mg
carboxylates, Zn carboxylates, Mg oxides, Zn oxides, Mg hydroxides,
Zn hydroxides, Mg carbonates and Zn carbonates.
16. A stabilizer mixture according to claim 1, which additionally
contains as a further component (X-1) a pigment or (X-2) an UV
absorber or (X-3) a pigment and an UV absorber.
17. A stabilizer mixture according to claim 1, which additionally
contains as a further component (XX) an organic salt of Ca, an
inorganic salt of Ca, Ca oxide or Ca hydroxide.
18. A composition comprising an organic material subject to
degradation induced by light, heat or oxidation and a stabilizer
mixture according to claim 1.
19. A composition according to claim 18 wherein the organic
material is a synthetic polymer.
20. A composition according to claim 18 wherein the organic
material is a polyolefin.
21. A composition according to claim 18 wherein the organic
material is polyethylene, polypropylene, a polyethylene copolymer
or a polypropylene copolymer.
22. (cancelled).
23. A method for stabilizing an organic material against
degradation induced by light, heat or oxidation, which comprises
incorporating into the organic material a stabilizer mixture
according to claim 1.
Description
[0001] The present invention relates to a stabilizer mixture
containing two different sterically hindered amine compounds and at
least one Mg- and/or Zn- compound, the use of this mixture for
stabilizing an organic material, in particular a polyolefin,
against degradation induced by light, heat or oxidation and the
organic material thus stabilized.
[0002] The stabilization of polyolefins is described in numerous
publications, for example in U.S. Pat. No. 4,929,652, U.S. Pat. No.
5,025,051, U.S. Pat. No. 5,037,870, EP-A-276,923, EP-A-290,388,
EP-A-429,731, EP-A-468,923, EP-A-661,341, EP-A-690,094,
DE-A-19,545,896 (Derwent 96-278,994/29; Chemical Abstracts
125:116779q), WO-A-95/25,767, GB-A-2,293,827, Chemical Abstracts
106:197407z, GB-A-2,332,678, WO-A-00/11,065, GB-A-2,316,409,
GB-A-2, 332,677, Chemical Abstracts 132: 335,575t and Research
Disclosure 34,549.
[0003] In more detail, the present invention relates to a
stabilizer mixture containing
[0004] (I) two different sterically hindered amine compounds,
and
[0005] (II) at least one compound selected from the group
consisting of an organic salt of Zn, an inorganic salt of Zn, Zn
oxide, Zn hydroxide, an organic salt of Mg, an inorganic salt of
Mg, Mg oxide and Mg hydroxide;
[0006] with the proviso that component (I) is different from the
combination of the compounds (B-8-a) and (B-8-b) 1
[0007] wherein n.sub.2 and n.sub.2* are a number from 2 to 50;
and
[0008] with the proviso that, when
[0009] component (I) is the combination of the compounds (B-1-a-1)
and (B-7-a); 2
[0010] wherein b.sub.1 is a number from 2 to 50, 3
[0011] wherein n.sub.1 is a number from 2 to 50; and,
[0012] at the same time, component (II) is a Zn carboxylate;
[0013] the stabilizer mixture additionally contains as a further
component
[0014] (X-1) a pigment or
[0015] (X-2) an UV absorber or
[0016] (X-3) a pigment and an UV absorber.
[0017] A preferred embodiment of the present invention relates to a
stabilizer mixture containing as component (I) two different
sterically hindered amine compounds wherein one sterically hindered
amine compound is a compound of the formula (B-1-b) or (B-1-d) 4
5
[0018] wherein b.sub.1 is a number from 2 to 20 and R.sub.6 is
hydrogen, C.sub.1-C.sub.8alkyl, O, --OH, --CH.sub.2CN,
C.sub.1-C.sub.18alkoxy, C.sub.5-C.sub.12cycloalkoxy,
C.sub.3-C.sub.6alkenyl, C.sub.7-C.sub.9phenylalkyl unsubstituted or
substituted on the phenyl by 1, 2 or 3 C.sub.1-C.sub.4alkyl; or
C.sub.1-C.sub.8acyl; and
[0019] the other sterically hindered amine compound is a compound
of the formula (B-7-a) 6
[0020] wherein n.sub.1 is a number from 2 to 20; and
[0021] component (II) is an organic salt of Zn, an inorganic salt
of Zn, Zn oxide or Zn hydroxide; preferably Zn carboxylate.
[0022] Preferably, a stabilizer mixture containing a compound of
the class (.beta.-1) as defined below, a compound of the class
(.beta.-7) as defined below and Zn-carboxylate, in particular an
organic salt of Zn, is disclaimed.
[0023] According to a preferred embodiment of the present
invention, component (II) is an organic salt of Mg, an inorganic
salt of Mg, Mg oxide or Mg hydroxide, when component (I) is the
combination of a compound of the class (.beta.-1) as defined below,
and a compound of the class (.beta.-7) as defined below.
[0024] The stabilizer mixtures according to the present invention
preferably do not contain a mineral oil.
[0025] The two different sterically hindered amine compounds of
component (I) are preferably selected from the group consisting of
the following classes
[0026] (.alpha.-1) a compound of the formula (A-1) 7
[0027] in which
[0028] E.sub.1 is hydrogen, C.sub.1-C.sub.8alkyl, O, --OH,
--CH.sub.2CN, C.sub.1-C.sub.18alkoxy, C.sub.5-C.sub.12cycloalkoxy,
C.sub.3-C.sub.6alkenyl, C.sub.7-C.sub.9phenylalkyl unsubstituted or
substituted on the phenyl by 1, 2 or 3 C.sub.1-C.sub.4alkyl; or
[0029] C.sub.1-C.sub.8acyl,
[0030] m.sub.1 is 1, 2 or 4,
[0031] if m.sub.1 is 1, E.sub.2 is C.sub.1-C.sub.25alkyl,
[0032] if m.sub.1 is 2, E.sub.2 is C.sub.1-C.sub.14alkylene or a
group of the formula (a-I) 8
[0033] wherein E.sub.3 is C.sub.1-C.sub.10alkyl or
C.sub.2-C.sub.10alkenyl, E.sub.4 is C.sub.1-C.sub.10alkylene,
and
[0034] E.sub.5 and E.sub.6 independently of one another are
C.sub.1-C.sub.4alkyl, cyclohexyl or methylcyclohexyl, and
[0035] if m.sub.1 is 4, E.sub.2 is
C.sub.4-C.sub.10alkanetetrayl;
[0036] (.alpha.-2) a compound of the formula (A-2) 9
[0037] in which
[0038] two of the radicals E.sub.7 are
--COO--(C.sub.1-C.sub.20alkyl), and
[0039] two of the radicals E.sub.7 are a group of the formula
(a-II) 10
[0040] with E.sub.8 having one of the meanings of E.sub.1;
[0041] (.alpha.-3) a compound of the formula (A-3) 11
[0042] in which
[0043] E.sub.9 and E.sub.10 together form
C.sub.2-C.sub.14alkylene,
[0044] E.sub.11 is hydrogen or a group -Z.sub.1-COO-Z.sub.2,
[0045] Z.sub.1 is C.sub.2-C.sub.14alkylene, and
[0046] Z.sub.2 is C.sub.1-C.sub.24alkyl, and
[0047] E.sub.12 has one of the meanings of E.sub.1;
[0048] (.alpha.-4) a compound of the formula (A-4) 12
[0049] wherein
[0050] the radicals E.sub.13 independently of one another have one
of the meanings of E.sub.1,
[0051] the radicals E.sub.14 independently of one another are
hydrogen or C.sub.1-C.sub.12alkyl, and
[0052] E.sub.15 is C.sub.1-C.sub.10alkylene or
C.sub.3-C.sub.10alkylidene;
[0053] (.alpha.-5) a compound of the formula (A-5) 13
[0054] wherein
[0055] the radicals E.sub.16 independently of one another have one
of the meanings of E.sub.1;
[0056] (.alpha.-6) a compound of the formula (A-6) 14
[0057] in which
[0058] E.sub.17 is C.sub.1-C.sub.24alkyl, and
[0059] E.sub.18 has one of the meanings of E.sub.1;
[0060] (.alpha.-7) a compound of the formula (A-7) 15
[0061] in which
[0062] E.sub.19, E.sub.20 and E.sub.21 independently of one another
are a group of the formula (a-III) 16
[0063] wherein E.sub.22 has one of the meanings of E.sub.1;
[0064] (.alpha.-8) a compound of the formula (A-8) 17
[0065] wherein
[0066] the radicals E.sub.23 independently of one another have one
of the meanings of E.sub.1, and E.sub.24 is hydrogen,
C.sub.1-C.sub.12alkyl or C.sub.1-C.sub.12alkoxy;
[0067] (.alpha.-9) a compound of the formula (A-9) 18
[0068] wherein
[0069] m.sub.2 is 1, 2 or 3,
[0070] E.sub.25 has one of the meanings of E.sub.1, and
[0071] when m.sub.2 is 1, E.sub.26 is a group 19
[0072] when m.sub.2 is 2, E.sub.26 is C.sub.2-C.sub.22alkylene,
and
[0073] when m.sub.2 is 3, E.sub.26 is a group of the formula (a-IV)
20
[0074] wherein the radicals E.sub.27 independently of one another
are C.sub.2-C.sub.12alkylene, and the radicals E.sub.28
independently of one another are C.sub.1-C.sub.12alkyl or
C.sub.5-C.sub.12cycloalkyl;
[0075] (.alpha.-10) a compound of the formula (A-10) 21
[0076] wherein
[0077] the radicals E.sub.29 independently of one another have one
of the meanings of E.sub.1, and
[0078] E.sub.30 is C.sub.2-C.sub.22alkylene,
C.sub.5-C.sub.7cycloalkylene,
Cl-C.sub.4alkylenedi(C.sub.5-C.sub.7cycloalkylene), phenylene or
phenylenedi(C.sub.1-C.sub.4alkylene);
[0079] (.beta.-1) a compound of the formula (B-1) 22
[0080] in which
[0081] R.sub.1, R.sub.3, R.sub.4 and R.sub.5 independently of one
another are hydrogen, C.sub.1-C.sub.12alkyl,
C.sub.5-C.sub.12cycloalkyl, C.sub.1-C.sub.4-alkyl-substituted
C.sub.5-C.sub.12cycloalkyl, phenyl, phenyl which is substituted by
--OH and/or C.sub.1-C.sub.10alkyl; C.sub.7-C.sub.9phenylalkyl,
C.sub.7-C.sub.9phenylalkyl which is substituted on the phenyl
radical by --OH and/or C.sub.1-C.sub.10alkyl; or a group of the
formula (b-I) 23
[0082] R.sub.2 is C.sub.2-C.sub.18alkylene,
C.sub.5-C.sub.7cycloalkylene or
C.sub.1-C.sub.4alkylenedi(B.sub.5-C.sub.7cycloalkylene), or
[0083] the radicals R.sub.1, R.sub.2 and R.sub.3, together with the
nitrogen atoms to which they are bonded, perform a 5- to
10-membered heterocyclic ring, or
[0084] R.sub.4 and R.sub.5, together with the nitrogen atom to
which they are bonded, form a 5- to 10-membered heterocyclic
ring,
[0085] R.sub.6 is hydrogen, C.sub.1-C.sub.8alkyl, O.sup.-, --OH,
--CH.sub.2CN, C.sub.1-C.sub.18alkoxy, C.sub.5-C.sub.12cycloalkoxy,
C.sub.3-C.sub.6alkenyl,
[0086] C.sub.7-C.sub.9phenylalkyl unsubstituted or substituted on
the phenyl by 1, 2 or 3 C.sub.1-C.sub.4alkyl; or
C.sub.1-C.sub.8acyl, and
[0087] b.sub.1 is a number from 2 to 50,
[0088] with the proviso that at least one of the radicals R.sub.1,
R.sub.3, R.sub.4 and R.sub.5 is a group of the formula (b-I);
[0089] (.beta.-2) a compound of the formula (B-2) 24
[0090] wherein
[0091] R.sub.7 and R.sub.11 independently of one another are
hydrogen or C.sub.1-C.sub.12alkyl,
[0092] R.sub.8, R.sub.9 and R.sub.10 independently of one another
are C.sub.2-C.sub.10alkylene, and
[0093] X.sub.1, X.sub.2, X.sub.3, X.sub.4, X.sub.5, X.sub.6,
X.sub.7 and X.sub.8 independently of one another are a group of the
formula (b-II), 25
[0094] in which R.sub.12 is hydrogen, C.sub.1-C.sub.12alkyl,
C.sub.5-C.sub.12cycloalkyl, C.sub.1-C.sub.4alkyl-substituted
C.sub.5-C.sub.12cycloalkyl, phenyl, --OH-- and/or
C.sub.1-C.sub.10alkyl-s- ubstituted phenyl,
C.sub.7-C.sub.9phenylalkyl, C.sub.7-C.sub.9phenylalkyl which is
substituted on the phenyl radical by --OH and/or
C.sub.1-C.sub.10alkyl; or a group of the formula (b-I) as defined
above, and
[0095] R.sub.13 has one of the meanings of R.sub.6;
[0096] (.beta.-3) a compound of the formula (B-3) 26
[0097] in which
[0098] R.sub.14 is C.sub.1-C.sub.10alkyl,
C.sub.5-C.sub.12cycloalkyl, C.sub.1-C.sub.4alkyl-substituted
C.sub.5-C.sub.12cycloalkyl, phenyl or
C.sub.1-C.sub.10alkyl-substituted phenyl,
[0099] R.sub.15 is C.sub.3-C.sub.10alkylene,
[0100] R.sub.16 has one of the meanings of R.sub.6, and
[0101] b.sub.2 is a number from 2 to 50;
[0102] (.beta.-4) a compound of the formula (B-4) 27
[0103] in which
[0104] R.sub.17 and R.sub.21 independently of one another are a
direct bond or a --N(X.sub.9)-CO-X.sub.10-CO--N(X.sub.11)- group,
where X.sub.9 and X.sub.11 independently of one another are
hydrogen, C.sub.1-C.sub.8alkyl, C.sub.5-C.sub.12cycloalkyl, phenyl,
C.sub.7-C.sub.9phenylalkyl or a group of the formula (b-I),
[0105] X.sub.10 is a direct bond or C.sub.1-C.sub.4alkylene,
[0106] R.sub.18 has one of the meanings of R.sub.6,
[0107] R.sub.19, R.sub.20, R.sub.23 and R.sub.24 independently of
one another are hydrogen, C.sub.1-C.sub.30alkyl,
C.sub.5-C.sub.12cycloalkyl or phenyl,
[0108] R.sub.22 is hydrogen, C.sub.1-C.sub.30alkyl,
C.sub.5-C.sub.12cycloalkyl, phenyl, C.sub.7-C.sub.9phenylalkyl or a
group of the formula (b-I), and
[0109] b.sub.3 is a number from 1 to 50;
[0110] (.beta.-5) a compound of the formula (B-5) 28
[0111] in which
[0112] R.sub.25, R.sub.26, R.sub.27, R.sub.28 and R.sub.29
independently of one another are a direct bond or
C.sub.1-C.sub.10alkylene,
[0113] R.sub.30 has one of the meanings of R.sub.6, and
[0114] b.sub.4 is a number from 1 to 50;
[0115] (.beta.-6) a product (B-6) obtainable by reacting a product,
obtained by reaction of a polyamine of the formula (B-6-1) with
cyanuric chloride, with a compound of the formula (B-6-2) 29
[0116] in which
[0117] b'.sub.5, b".sub.5 and b'".sub.5 independently of one
another are a number from 2 to 12,
[0118] R.sub.31 is hydrogen, C.sub.1-C.sub.12alkyl,
C.sub.5-C.sub.12cycloalkyl, phenyl or C.sub.7-C.sub.9phenylalkyl,
and
[0119] R.sub.32 has one of the meanings of R.sub.6;
[0120] (.beta.-7) a compound of the formula (B-7) 30
[0121] wherein A.sub.1 is hydrogen or C.sub.1-C.sub.4alkyl,
[0122] A.sub.2 is a direct bond or C.sub.1-C.sub.10alkylene,
and
[0123] n.sub.1 is a number from 2 to 50;
[0124] (.beta.-8) at least one compound of the formulae (B-8-a) and
(B-8-b) 31 32
[0125] wherein n.sub.2 and n.sub.2* are a number from 2 to 50;
[0126] (.beta.-9) a compound of the formula (B-9) 33
[0127] wherein A.sub.3 and A.sub.4 independently of one another are
hydrogen or C.sub.1-C.sub.8alkyl, or A.sub.3 and A.sub.4 together
form a C.sub.2-C.sub.14alkylene group, and
[0128] the variables n.sub.3 independently of one another are a
number from 1 to 50; and
[0129] (.beta.-10) a compound of the formula (B-10) 34
[0130] wherein n.sub.4 is a number from 2 to 50,
[0131] A.sub.5 is hydrogen or C.sub.1-C.sub.4alkyl,
[0132] the radicals A.sub.6 and A.sub.7 independently of one
another are C.sub.1-C.sub.4alkyl or a group of the formula
(b-I),
[0133] with proviso that at least 50% of the radicals A.sub.7 are a
group of the formula (b-I).
[0134] Examples of component (I) are:
[0135] A compound selected from the class .alpha.-1 and a compound
selected from the class .alpha.-3, .alpha.-5, .alpha.-6, .alpha.-7,
.alpha.-9, .alpha.-10, .beta.-1, .beta.-2, .beta.-3, .beta.-4,
.beta.-5, .beta.-6, .beta.-7, .beta.-8 or .beta.-9.
[0136] A compound selected from the class .alpha.-3 and a compound
selected from the class .alpha.-5, .alpha.-6, .alpha.-7, .alpha.-9,
.alpha.-10, .beta.-1, .beta.-2, .beta.-3, .beta.-4, .beta.-5,
.beta.-6, .beta.-7, .beta.-8 or .beta.-9.
[0137] A compound selected from the class .alpha.-5 and a compound
selected from the class .alpha.-6, .alpha.-7, .alpha.-9,
.alpha.-10, .beta.-1, .beta.-2, .beta.-3, .beta.-4, .beta.-5,
.beta.-6, .beta.-7, .beta.-8 or .beta.-9.
[0138] A compound selected from the class .alpha.-6 and a compound
selected from the class .alpha.-9, .alpha.-10, .beta.-1, .beta.-2,
.beta.-3, .beta.-4, .beta.-5, .beta.-6, .beta.-7, .beta.-8 or
.beta.-9.
[0139] A compound selected from the class .alpha.-7 and a compound
selected from the class .alpha.-9, .alpha.-10, .beta.-1, .beta.-2,
.beta.-3, .beta.-4, .beta.-5, .beta.-6, .beta.-7, .beta.-8 or
.beta.-9.
[0140] A compound selected from the class .alpha.-10 and a compound
selected from the class .beta.-1, .beta.-2, .beta.-3, .beta.-4,
.beta.-5, .beta.-6, .beta.-7, .beta.-8 or .beta.-9.
[0141] A compound selected from the class .beta.-1 and a compound
selected from the class .beta.-2, .beta.-3, .beta.-4, .beta.-5,
.beta.-6, .beta.-7, .beta.-8, .beta.-9 or .beta.-10.
[0142] A compound selected from the class .beta.-2 and a compound
selected from the class .beta.-3, .beta.-4, .beta.-5, .beta.-6,
.beta.-7, .beta.-8, .beta.-9 or .beta.-10.
[0143] A compound selected from the class .beta.-3 and a compound
selected from the class .beta.-4, .beta.-5, .beta.-6, .beta.-7,
.beta.-8, .beta.-9 or .beta.-10.
[0144] A compound selected from the class .beta.-4 and a compound
selected from the class .beta.-5, .beta.-6, .beta.-7, .beta.-8,
.beta.-9 or .beta.-10.
[0145] A compound selected from the class .beta.-5 and a compound
selected from the class .beta.-6, .beta.-7, .beta.-8, .beta.-9 or
.beta.-10.
[0146] A compound selected from the class .beta.-6 and a compound
selected from the class .beta.-7, .beta.-8, .beta.-9 or
.beta.-10.
[0147] A compound selected from the class .beta.-7 and a compound
selected from the class .beta.-8, .beta.-9 or .beta.-10.
[0148] A compound selected from the class .beta.-8 and a compound
selected from the class .beta.-9 or .beta.-10.
[0149] A compound selected from the class .beta.-9 and a compound
selected from the class .beta.-10.
[0150] According to a preferred embodiment,
[0151] the two different sterically hindered amine compounds of
component (I) are selected from the group consisting of the classes
(.alpha.-1), (.alpha.-2), (.alpha.-3), (.alpha.-4), (.alpha.-5),
(.alpha.-6), (.alpha.-7), (.alpha.-8), (.alpha.-9) and
(.alpha.-10).
[0152] According to a further preferred embodiment,
[0153] the two different sterically hindered amine compounds of
component (I) are selected from the group consisting of the classes
(.beta.-1), (.beta.-2), (.beta.-3), (.beta.-4), (.beta.-5),
(.beta.-6), (.beta.-7), (.beta.-8), (.beta.-9) and (.beta.-10).
[0154] According to another preferred embodiment,
[0155] one of the two different sterically hindered amine compounds
of component (I) is selected from the group consisting of the
classes (.alpha.-1), (.alpha.-2), (.alpha.-3), (.alpha.-4),
(.alpha.-5), (.alpha.-6), (.alpha.-7), (.alpha.-8), (.alpha.-9) and
(.alpha.-10), and
[0156] the other of the two different sterically hindered amine
compounds of component (I) is selected from the group consisting of
the classes (.beta.-1), (.beta.-2), (.beta.-3), (.beta.-4),
(.beta.-5), (.beta.-6), (.beta.-7), (.beta.-8), (.beta.-9) and
(.beta.-10).
[0157] One of the two different sterically hindered amine compounds
of component (I) is preferably selected from the class
(.beta.-1).
[0158] According to a particularly preferred embodiment,
[0159] one of the two different sterically hindered amine compounds
of component (I) is selected from the class (.beta.-1), and
[0160] the other of the two different sterically hindered amine
compounds of component (I) is selected from the class (.alpha.-1)
or (.beta.-7).
[0161] According to another particularly preferred embodiment,
[0162] one of the two different sterically hindered amine compounds
of component (I) is selected from the class (.beta.-7), and
[0163] the other of the two different sterically hindered amine
compounds of component (I) is selected from the class
(.beta.-2).
[0164] The two different sterically hindered amine compounds of
component (I) are preferably selected from different classes.
[0165] Examples of alkyl having up to 30 carbon atoms are methyl,
ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl,
2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl,
1,3-dimethyl-butyl, 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,
nonyl, decyl, undecyl, 1-methylundecyl, dodecyl,
1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl,
hexadecyl, heptadecyl, octadecyl, eicosyl, docosyl and triacontyl.
One of the preferred definitions of E.sub.1, E.sub.8, E.sub.12,
E.sub.13, E.sub.16, E.sub.18, E.sub.22, E.sub.23, E.sub.25,
E.sub.29, R.sub.6, R.sub.13, R.sub.16, R.sub.18, R.sub.30 and
R.sub.32 is C.sub.1-C.sub.4alkyl, especially methyl. R.sub.31 is
preferably butyl.
[0166] Examples of alkoxy having up to 18 carbon atoms are methoxy,
ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy,
isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy,
tetradecyloxy, hexadecyloxy and octadecyloxy. One of the preferred
meanings of E.sub.1 is octoxy. E.sub.24 is preferably
C.sub.1-C.sub.4alkoxy and one of the preferred meanings of R.sub.6
is propoxy.
[0167] Examples of C.sub.5-C.sub.12cycloalkyl are cyclopentyl,
cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl.
C.sub.5-C.sub.8Cycloalkyl, especially cyclohexyl, is preferred.
[0168] C.sub.1-C.sub.4Alkyl-substituted C.sub.5-C.sub.12cycloalkyl
is for example methylcyclohexyl or dimethylcyclohexyl.
[0169] Examples of C.sub.5-C.sub.12cycloalkoxy are cyclopentoxy,
cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy and
cyclododecyloxy. C.sub.5-C.sub.8Cycloalkoxy, in particular
cyclopentoxy and cyclohexoxy, is preferred.
[0170] --OH-- and/or C.sub.1-C.sub.10alkyl-substituted phenyl is
for example methylphenyl, dimethylphenyl, trimethylphenyl,
tert-butylphenyl or 3,5-di-tert-butyl-4-hydroxyphenyl.
[0171] Examples of C.sub.7-C.sub.9phenylalkyl are benzyl and
phenylethyl.
[0172] C.sub.7-C.sub.9Phenylalkyl which is substituted on the
phenyl radical by --OH and/or by alkyl having up to 10 carbon atoms
is for example methylbenzyl, dimethylbenzyl, trimethylbenzyl,
tert-butylbenzyl or 3,5-di-tert-butyl-4-hydroxybenzyl.
[0173] Examples of alkenyl having up to 10 carbon atoms are allyl,
2-methallyl, butenyl, pentenyl and hexenyl. Allyl is preferred. The
carbon atom in position 1 is preferably saturated.
[0174] Examples of acyl containing not more than 8 carbon atoms are
formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl,
octanoyl, acryloyl, methacryloyl and benzoyl.
C.sub.1-C.sub.8Alkanoyl, C.sub.3-C.sub.8alkenyl and benzoyl are
preferred. Acetyl and acryloyl are especially preferred.
[0175] Examples of alkylene having up to 22 carbon atoms are
methylene, ethylene, propylene, trimethylene, tetramethylene,
pentamethylene, 2,2-dimethyltrimethylene, hexamethylene,
trimethylhexamethylene, octamethylene and decamethylene.
[0176] An example of C.sub.3-C.sub.10alkylidene is the group 35
[0177] An example of C.sub.4-C.sub.10alkanetetrayl is
1,2,3,4-butanetetrayl.
[0178] An example of C.sub.5-C.sub.7cycloalkylene is
cyclohexylene.
[0179] An example of
C.sub.1-C.sub.4alkylenedi(C.sub.5-C.sub.7cycloalkylen- e) is
methylenedicyclohexylene.
[0180] An example of phenylenedi(C.sub.1-C.sub.4alkylene) is
methylene-phenylene-methylene or ethylene-phenylene-ethylene.
[0181] Where the radicals R.sub.1, R.sub.2 and R.sub.3, together
with the nitrogen atoms to which they are attached, form a 5- to
10-membered heterocyclic ring, this ring is for example 36
[0182] A 6-membered heterocyclic ring is preferred.
[0183] Where the radicals R.sub.4 and R.sub.5, together with the
nitrogen atom to which they are attached, form a 5- to 10-membered
heterocyclic ring, this ring is for example 1-pyrrolidyl,
piperidino, morpholino, 1-piperazinyl, 4-methyl-1-piperazinyl,
1-hexahydroazepinyl, 5,5,7-trimethyl-1-homopiperazinyl or
4,5,5,7-tetramethyl-1-homopiperaziny- l. Morpholino is particularly
preferred.
[0184] One of the preferred definitions of R.sub.19 and R.sub.23 is
phenyl.
[0185] R.sub.26 is preferably a direct bond.
[0186] n.sub.1, n.sub.2, n.sub.2* and n.sub.4 are preferably a
number from 2 to 25, in particular 2 to 20. n.sub.3 is preferably a
number from 1 to 25, in particular 1 to 20.
[0187] b.sub.1 and b.sub.2 are preferably a number from 2 to 25, in
particular 2 to 20.
[0188] b.sub.3 and b.sub.4 are preferably a number from 1 to 25, in
particluar 1 to 20.
[0189] b'.sub.5 and b'".sub.5 are preferably 3 and b".sub.5 is
preferably 2.
[0190] The compounds described above as components (I) and (II) are
essentially known and commercially available. All of them can be
prepared by known processes.
[0191] The preparation of the compounds of component (I) is
disclosed, for example, in
[0192] U.S. Pat. No. 5,679,733, U.S. Pat. No. 3,640,928, U.S. Pat.
No. 4,198,334, U.S. Pat. No. 5,204,473, U.S. Pat. No. 4,619,958,
U.S. Pat. No. 4,110,306, U.S. Pat. No. 4,110,334, U.S. Pat. No.
4,689,416, U.S. Pat. No. 4,408,051, U.S. Pat. No. 768,175 (Derwent
88-138,751/20), U.S. Pat. No. 5,049,604, U.S. Pat. No. 4,769,457,
U.S. Pat. No. 4,356,307, U.S. Pat. No. 4,619,956, U.S. Pat. No.
5,182,390, GB-A-2,269,819, U.S. Pat. No. 4,292,240, U.S. Pat. No.
5,026,849, U.S. Pat. No. 5,071,981, U.S. Pat. No. 4,547,538, U.S.
Pat. No. 4,976,889, U.S. Pat. No. 4,086,204, U.S. Pat. No.
6,046,304, U.S. Pat. No. 4,331,586, U.S. Pat. No. 4,108,829, U.S.
Pat. No. 5,051,458, WO-A-94/12,544 (Derwent 94-177,274/22),
DD-A-262,439 (Derwent 89-122,983/17), U.S. Pat. No. 4,857,595, U.S.
Pat. No. 4,529,760, U.S. Pat. No. 4,477,615, CAS 136,504-96-6, U.S.
Pat. No. 4,233,412, U.S. Pat. No. 4,340,534, WO-A-98/51,690 and
EP-A-1,803.
[0193] The product (B-6) can be prepared analogously to known
processes, for example by reacting a polyamine of formula (B-6-1)
with cyanuric chloride in a molar ratio of from 1:2 to 1:4 in the
presence of anhydrous lithium carbonate, sodium carbonate or
potassium carbonate in an organic solvent such as
1,2-dichloroethane, toluene, xylene, benzene, dioxane or tert-amyl
alcohol at a temperature of from -20.degree. C. to +10.degree. C.,
preferably from -10.degree. C. to +10.degree. C., in particular
from 0.degree. C. to +10.degree. C., for from 2 to 8 hours,
followed by reaction of the resultant product with a
2,2,6,6-tetramethyl-4-piperidyla- mine of the formula (B-6-2). The
molar ratio of the 2,2,6,6-tetramethyl-4-piperidylamine to
polyamine of the formula (B-6-1) employed is for example from 4:1
to 8:1. The quantity of the 2,2,6,6-tetramethyl-4-piperidylamine
can be added in one portion or in more than one portion at
intervals of a few hours.
[0194] The molar ratio of polyamine of the formula (B-6-1) to
cyanuric chloride to 2,2,6,6-tetramethyl-4-piperidylamine of the
formula (B-6-2) is preferably from 1:3:5 to 1:3:6.
[0195] The following example indicates one way of preparing a
preferred product (B-6-a).
EXAMPLE
[0196] 23.6 g (0.128 mol) of cyanuric chloride, 7.43 g (0.0426 mol)
of N,N'-bis [3-aminopropyl]ethylenediamine and 18 g (0.13 mol) of
anhydrous potassium carbonate are reacted at 5.degree. C. for 3
hours with stirring in 250 ml of 1,2-dichloroethane. The mixture is
warmed at room temperature for a further 4 hours. 27.2 g (0.128
mol) of N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine are added and
the resultant mixture is warmed at 60.degree. C. for 2 hours. A
further 18 g (0.13 mol) of anhydrous potassium carbonate are added
and the mixture is warmed at 60.degree. C. for a further 6 hours.
The solvent is removed by distillation under a slight vacuum (200
mbar) and replaced by xylene. 18.2 g (0.085 mol) of
N-(2,2,6,6-tetramethyl-4-piperidyl) butylamine and 5.2 g (0.13 mol)
of ground sodium hydroxide are added, the mixture is heated at
reflux for 2 hours and, for a further 12 hours, the water formed
during the reaction is removed by azeotropic distillation. The
mixture is filtered. The solution is washed with water and dried
over Na.sub.2SO.sub.4. The solvent is evaporated and the residue is
dried at 120-130.degree. C. in vacuo (0.1 mbar). The desired
product is obtained as a colourless resin.
[0197] In general, the product (B-6) can, for example, be
represented by a compound of the formula (B-6-.alpha.),
(B-6-.beta.) or (B-6-.gamma.). It can also be in the form of a
mixture of these three compounds. 37 38
[0198] A preferred meaning of the formula (B-6-.alpha.) is 39
[0199] A preferred meaning of the formula (B-6-.beta.) is 40
[0200] A preferred meaning of the formula (B-6-.gamma.) is 41
[0201] In the above formulae (B-6-.alpha.) to (B-6-.gamma.),
b.sub.5 is preferably 2 to 20, in particular 2 to 10.
[0202] The two different sterically hindered amine compounds of
component (I) are preferably selected from the group consisting of
the following commercial products:
[0203] DASTIB 845 (RTM), TINUVIN 770 (RTM), TINUVIN 765 (RTM),
TINUVIN 144 (RTM), TINUVIN 123 (RTM), MARK LA 52 (RTM), MARK LA 57
(RTM), MARK LA 62 (RTM), MARK LA 67 (RTM), HOSTAVIN N 20 (RTM),
HOSTAVIN N 24 (RTM), SANDUVOR 3050 (RTM), DIACETAM 5 (RTM),
SUMISORB TM 61 (RTM), UVINUL 4049 (RTM), SANDUVOR PR 31 (RTM),
GOODRITE UV 3034 (RTM), GOODRITE UV 3150 (RTM), GOODRITE UV 3159
(RTM), GOODRITE 3110 x 128 (RTM), UVINUL 4050 H (RTM), CHIMASSORB
944 (RTM), CHIMASSORB 2020 (RTM), CYASORB UV 3346 (RTM), CYASORB UV
3529 (RTM), DASTIB 1082 (RTM), CHIMASSORB 119 (RTM), UVASIL 299
(RTM), UVASIL 125 (RTM), UVASIL 2000 (RTM), UVINUL 5050 H (RTM),
LICHTSCHUTZSTOFF UV 31 (RTM), LUCHEM HA B 18 (RTM), MARK LA 63
(RTM), MARK LA 68 (RTM), UVASORB HA 88 (RTM), TINUVIN 622 (RTM),
HOSTAVIN N 30 (RTM) and FERRO AM 806 (RTM).
[0204] The meanings of the terminal groups which saturate the free
valences in the compounds of the formulae (B-1), (B-3), (B-4),
(B-5), (B-6-.alpha.), (B-6-.beta.), (B-6-.gamma.), (B-7), (B-8-a),
(B-8-b) and (B-10) depend on the processes used for their
preparation. The terminal groups can also be modified after the
preparation of the compounds.
[0205] If the compounds of the formula (B-1) are prepared by
reacting a compound of the formula 42
[0206] in which X is, for example, halogen, in particular chlorine,
and R.sub.4 and R.sub.5 are as defined above, with a compound of
the formula 43
[0207] in which R.sub.1, R.sub.2 and R.sub.3 are as defined above,
the terminal group bonded to the diamino radical is hydrogen or
44
[0208] and the terminal group bonded to the triazine radical is X
or 45
[0209] If X is halogen, it is advantageous to replace this, for
example, by --OH or an amino group when the reaction is complete.
Examples of amino groups which may be mentioned are
pyrrolidin-1-yl, morpholino, --NH.sub.2,
--N(C.sub.1-C.sub.8)alkyl).sub.2 and --NR(C.sub.1-C.sub.8alky- l),
in which R is hydrogen or a group of the formula (b-I).
[0210] The compounds of the formula (B-1) also cover compounds of
the formula 46
[0211] wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5 and
b.sub.1 are as defined above and R.sub.4* has one of the meanings
of R.sub.4 and R.sub.5* has one of the meanings of R.sub.5.
[0212] One of the particularly preferred compounds of the formula
(B-1) is 47
[0213] The preparation of this compound is described in Example 10
of U.S. Pat. No. 6,046,304.
[0214] In the compounds of the formula (B-3), the terminal group
bonded to the silicon atom can be, for example,
(R.sub.14).sub.3Si--O--, and the terminal group bonded to the
oxygen can be, for example, --Si(R.sub.14).sub.3.
[0215] The compounds of the formula (B-3) can also be in the form
of cyclic compounds if b.sub.2 is a number from 3 to 10, i.e. the
free valences shown in the structural formula then form a direct
bond.
[0216] In the compounds of the formula (B-4), the terminal group
bonded to the 2,5-dioxopyrrolidine ring is, for example, hydrogen,
and the terminal group bonded to the --C(R.sub.23)(R.sub.24)-
radical is, for example, 48
[0217] In the compounds of the formula (B-5), the terminal group
bonded to the carbonyl radical is, for example, 49
[0218] and the terminal group bonded to the oxygen radical is, for
example, 50
[0219] In the compounds of the formulae (B-6-.alpha.), (B-6-.beta.)
and (B-6-.gamma.), the terminal group bonded to the triazine
radical is, for example, Cl or a 51
[0220] group, and the terminal group bonded to the amino radical
is, for example, hydrogen or a 52
[0221] group.
[0222] If the compounds of the formula (B-7) are prepared, for
example, by reacting a compound of the formula 53
[0223] in which A.sub.1 is hydrogen or methyl, with a dicarboxylic
acid diester of the formula Y--OOC-A.sub.2-COO--Y, in which Y is,
for example, methyl, ethyl or propyl, and A.sub.2 is as defined
above, the terminal group bonded to the
2,2,6,6-tetramethyl-4-oxypiperidin-1 -yl radical is hydrogen or
--CO-A.sub.2-COO--Y, and the terminal group bonded to the diacyl
radical is --O--Y or 54
[0224] In the compounds of the formula (B-8-a), the terminal group
bonded to the nitrogen can be, for example, hydrogen and the
terminal group bonded to the 2-hydroxypropylene radical can be, for
example, a 55
[0225] group.
[0226] In the compounds of the formula (B-8-b), the terminal group
bonded to the dimethylene radical can be, for example, --OH, and
the terminal group bonded to the oxygen can be, for example,
hydrogen. The terminal groups can also be polyether radicals.
[0227] In the compounds of the formula (B-10), the end group bonded
to the --CH.sub.2-- residue can be, for example, hydrogen and the
end group bonded to the --CH(CO.sub.2A.sub.7) residue can be, for
example, --CH.dbd.CH--COOA.sub.7.
[0228] E.sub.1, E.sub.8, E.sub.12, E.sub.13, E.sub.16, E.sub.18,
E.sub.22, E.sub.23, E.sub.25, E.sub.29, R.sub.6, R.sub.13,
R.sub.16, R.sub.18, R30 and R.sub.32 are preferably hydrogen,
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.10alkoxy, cyclohexyloxy, allyl,
benzyl or acetyl.
[0229] E.sub.1, E.sub.8, E.sub.12, E.sub.13, E.sub.16, E.sub.18,
E.sub.22, E.sub.23, E.sub.25, E.sub.29, R.sub.6, R.sub.13,
R.sub.16, R.sub.18, R.sub.30 and R.sub.32 are in particular
hydrogen or methyl and E.sub.1 and R.sub.6 additionally are
C.sub.1-C.sub.8alkoxy.
[0230] According to a preferred embodiment,
[0231] m.sub.1 is 1, 2 or 4,
[0232] if m.sub.1 is 1, E.sub.2 is C.sub.12-C.sub.20alkyl,
[0233] if m.sub.1 is 2, E.sub.2 is C.sub.2-C.sub.10alkylene or a
group of the formula (a-I)
[0234] E.sub.3 is C.sub.1-C.sub.4alkyl,
[0235] E.sub.4 is C.sub.1-C.sub.6alkylene, and
[0236] E.sub.5 and E.sub.6 independently of one another are
C.sub.1-C.sub.4alkyl, and
[0237] if m.sub.1 is 4, E.sub.2 is
C.sub.4-C.sub.8alkanetetrayl;
[0238] two of the radicals E.sub.7 are
--COO--(C.sub.10-C.sub.15alkyl), and
[0239] two of the radicals E.sub.7 are a group of the formula
(a-II);
[0240] E.sub.9 and E.sub.10 together form
C.sub.9-C.sub.13alkylene,
[0241] E.sub.11 is hydrogen or a group -Z.sub.1-COO-Z.sub.2,
[0242] Z.sub.1 is C.sub.2-C.sub.6alkylene, and
[0243] Z.sub.2 is C.sub.10-C.sub.16alkyl;
[0244] E.sub.14 is hydrogen, and
[0245] E.sub.15 is C.sub.2-C.sub.6alkylene or
C.sub.3-C.sub.5alkylidene;
[0246] E.sub.17 is C.sub.10-C.sub.14alkyl;
[0247] E.sub.24 is C.sub.1-C.sub.4alkoxy;
[0248] m.sub.2 is 1, 2 or 3,
[0249] when m.sub.2 is 1, E.sub.26 is a group 56
[0250] when m.sub.2 is 2, E.sub.26 is C.sub.2-C.sub.6alkylene,
and
[0251] when m.sub.2 is 3, E.sub.26 is a group of the formula
(a-IV)
[0252] the radicals E.sub.27 independently of one another are
C.sub.2-C.sub.6alkylene, and
[0253] the radicals E.sub.28 independently of one another are
C.sub.1-C.sub.4alkyl or C.sub.5-C.sub.8cycloalkyl; and
[0254] E.sub.30 is C.sub.2-C.sub.8alkylene;
[0255] R.sub.1 and R.sub.3 independently of one another are a group
of the formula (b-I),
[0256] R.sub.2 is C.sub.2-C.sub.8alkylene,
[0257] R.sub.4 and R.sub.5 independently of one another are
hydrogen, C.sub.1-C.sub.12alkyl, C.sub.5-C.sub.8cycloalkyl or a
group of the formula (b-I), or the radicals R.sub.4 and R.sub.5,
together with the nitrogen atom to which they are bonded, form a 5-
to 10-membered heterocyclic ring, and b.sub.1 is a number from 2 to
25;
[0258] R.sub.7 and R.sub.11 independently of one another are
hydrogen or C.sub.1-C.sub.4alkyl,
[0259] R.sub.8, R.sub.9 and R.sub.10 independently of one another
are C.sub.2-C.sub.4alkylene, and
[0260] X.sub.1, X.sub.2, X.sub.3, X.sub.4, X.sub.5, X.sub.6,
X.sub.7 and X.sub.8 independently of one another are a group of the
formula (b-II),
[0261] R.sub.12 is hydrogen, C.sub.1-C.sub.4alkyl,
C.sub.5-C.sub.8cycloalk- yl or a group of the formula (b-I);
[0262] R.sub.14 is C.sub.1-C.sub.4alkyl,
[0263] R.sub.15 is C.sub.3-C.sub.6alkylene, and
[0264] b.sub.2 is a number from 2 to 25;
[0265] R.sub.17 and R.sub.21 independently of one another are a
direct bond or a group
--N(X.sub.9)-CO-X.sub.10-CO--N(X.sub.11)-,
[0266] X.sub.9 and X.sub.11 independently of one another are
hydrogen or C.sub.1-C.sub.4alkyl,
[0267] X.sub.10 is a direct bond,
[0268] R.sub.19 and R.sub.23 are C.sub.1-C.sub.25alkyl or
phenyl,
[0269] R.sub.20 and R.sub.24 are hydrogen or
C.sub.1-C.sub.4alkyl,
[0270] R.sub.22 is C.sub.1-C.sub.25alkyl or a group of the formula
(b-I), and
[0271] b.sub.3 is a number from 1 to 25;
[0272] R.sub.25, R.sub.26, R.sub.27, R.sub.28 and R.sub.29
independently of one another are a direct bond or
C.sub.1-C.sub.4alkylene, and
[0273] b.sub.4 is a number from 1 to 25;
[0274] b'.sub.5, b".sub.5 and b'".sub.5 independently of one
another are a number from 2 to 4, and
[0275] R.sub.31 is hydrogen, C.sub.1-C.sub.4alkyl,
C.sub.5-C.sub.8cycloalk- yl, phenyl or benzyl;
[0276] A.sub.1 is hydrogen or methyl,
[0277] A.sub.2 is a direct bond or C.sub.2-C.sub.6alkylene, and
[0278] n.sub.1 is a number from 2 to 25;
[0279] n.sub.2 and n.sub.2* are a number from 2 to 25;
[0280] A.sub.3 and A.sub.4 independently of one another are
hydrogen or C.sub.1-C.sub.4alkyl, or A.sub.3 and A.sub.4 together
form a C.sub.9-C.sub.13alkylene group, and
[0281] the variables n.sub.3 independently of one another are a
number from 1 to 25;
[0282] n.sub.4 is a number from 2 to 25,
[0283] A.sub.5 and A.sub.6 independently of one another are
C.sub.1-C.sub.4alkyl, and
[0284] A.sub.7 is C.sub.1-C.sub.4alkyl or a group of the formula
(b-I)
[0285] with the proviso that at least 50% of the radicals A.sub.7
are a group of the formula (b-I).
[0286] The two different sterically hindered amine compounds of
component (I) are preferably selected from the group consisting of
the compounds of the formulae (A-1-a), (A-1-b), (A-1-c), (A-1-d),
(A-2-a), (A-3-a), (A-3-b), (A-4-a), (A-4-b), (A-5), (A-6-a), (A-7),
(A-8-a), (A-9-a), (A-9-b), (A-9-c), (A-10-a), (B-1-a), (B-1-b),
(B-1-c), (B-1-d), (B-2-a), (B-3-a), (B-4-a), (B-4-b) and (B-4-c), a
product (B-6-a) and the compounds of the formulae (B-7-a), (B-8-a),
(B-8-b), (B-9-a) and (B-10-a); 57
[0287] wherein E.sub.1 is hydrogen, C.sub.1-C.sub.8alkyl, O.sup.-,
--OH, --CH.sub.2CN, C.sub.1-C.sub.18alkoxy,
C.sub.5-C.sub.12cycloalkoxy, C.sub.3-C.sub.6alkenyl,
C.sub.7-C.sub.9phenylalkyl unsubstituted or substituted on the
phenyl by 1, 2 or 3 C.sub.1-C.sub.4alkyl; or C.sub.1-C.sub.8acyl;
58
[0288] in which two of the radicals E.sub.7 are
--COO--C.sub.13H.sub.27 and
[0289] two of the radicals E.sub.7 are 59
[0290] and E.sub.8 has one of the meanings 60
[0291] wherein E.sub.12 has one of the meanings of E.sub.1; 61
[0292] wherein E.sub.13 has one of the meanings of E.sub.1; 62
[0293] wherein E.sub.16 has one of the meanings of E.sub.1; 63
[0294] wherein E.sub.18 has one of the meanings of E.sub.1; 64
[0295] in which E.sub.19, E.sub.20 and E.sub.21 independently of
one another are a group of the formula (a-III) 65
[0296] wherein E.sub.22 has one of the meanings of E.sub.1; 66
[0297] wherein E.sub.23 has one of the meanings of E.sub.1; 67
[0298] wherein E.sub.25 has one of the meanings of E.sub.1; 68
[0299] wherein E.sub.29 has one of the meanings of E.sub.1; 69
[0300] wherein b.sub.1 is a number from 2 to 20 and R.sub.6 is
hydrogen, C.sub.1-C.sub.8alkyl, O.sup.-, --OH, --CH.sub.2CN,
C.sub.1-C.sub.18alkoxy, C.sub.5-C.sub.12cycloalkoxy,
C.sub.3-C.sub.6alkenyl, C.sub.7-C.sub.9phenylalkyl unsubstituted or
substituted on the phenyl by 1, 2 or 3 C.sub.1-C.sub.4alkyl; or
C.sub.1-C.sub.8acyl; 70
[0301] wherein R.sub.13 has one of the meanings of R.sub.6, 71
[0302] wherein b.sub.2 is a number from 2 to 20 and R.sub.16 has
one of the meanings of R.sub.6; 72
[0303] wherein b.sub.3 is a number from 1 to 20 and R.sub.18 has
one of the meanings of R.sub.6; 73
[0304] wherein b.sub.4 is a number from 1 to 20 and R.sub.30 has
one of the meanings of R.sub.6;
[0305] a product (B-6-a) obtainable by reacting a product, obtained
by reaction of a polyamine of the formula (B-6-1-a) with cyanuric
chloride, with a compound of the formula (B-6-2-a) 74
[0306] in which R.sub.32 has one of the meanings of R.sub.6; 75
[0307] wherein n.sub.1 is a number from 2 to 20; 76
[0308] wherein n.sub.2 and n.sub.2* are a number from 2 to 20;
77
[0309] wherein the variables n.sub.3 independently of one another
are a number from 1 to 20; 78
[0310] wherein n.sub.4 is a number from 2 to 20, and
[0311] at least 50% of the radicals A.sub.7 are a group of the
formula (b-I) 79
[0312] wherein R.sub.6 is hydrogen, C.sub.1-C.sub.8alkyl, O.sup.-,
--OH, --CH.sub.2CN, C.sub.1-C.sub.18alkoxy,
C.sub.5-C.sub.12cycloalkoxy, C.sub.3-C.sub.6alkenyl,
C.sub.7-C.sub.9phenylalkyl unsubstituted or substituted on the
phenyl by 1, 2 or 3 C.sub.1-C.sub.4alkyl; or
C.sub.1-C.sub.8acyl,
[0313] and the remaining radicals A.sub.7 are ethyl.
[0314] According to a preferred embodiment, the two different
sterically hindered amine compounds of component (I) are
[0315] 1) a compound of the formula (A-1-b) wherein E.sub.1 is
hydrogen, and a compound of the formula (B-1-a) wherein R.sub.6 is
hydrogen;
[0316] 2) a compound of the formula (B-1-a) wherein R.sub.6 is
hydrogen, and a compound of the formula (B-7-a); or
[0317] 3) a compound of the formula (B-2-a) wherein R.sub.13 is
methyl, and a compound of the formula (B-7-a).
[0318] The organic salt of zinc or magnesium defined in component
(II) is preferably a compound of the formula MeL.sub.2 in which Me
is zinc or magnesium and L is an anion of an organic acid or of an
enol. The organic acid can, for example, be a sulfonic acid,
sulfinic acid, phosphonic acid or phosphinic acid, but is
preferably a carboxylic acid. The acid can be aliphatic, aromatic,
araliphatic or cycloaliphatic; it can be linear or branched; it can
be substituted by hydroxyl or alkoxy groups; it can be saturated or
unsaturated and it preferably contains 1 to 24 carbon atoms.
[0319] Examples of carboxylic acids of this type are formic,
acetic, propionic, butyric, isobutyric, caprioic, 2-ethylcaproic,
caprylic, capric, lauric, palmitic, stearic, behenic, oleic,
lactic, ricinoleic, 2-ethoxypropionic, benzoic, salicylic,
4-butylbenzoic, toluic, 4-dodecylbenzoic, phenylacetic,
naphthylacetic, cyclohexanecarboxylic, 4-butylcyclohexanecarboxylic
or cyclohexylacetic acid. The carboxylic acid can also be a
technical mixture of carboxylic acids, for example technical
mixtures of fatty acids or mixtures of alkylated benzoic acids.
[0320] Examples of organic acids containing sulfur or phosphorus
are methanesulfonic, ethanesulfonic,
.alpha.,.alpha.-dimethylethanesulfonic, n-butanesulfonic,
n-dodecanesulfonic, benzenesulfonic, toluenesulfonic,
4-nonylbenzenesulfonic, 4-dodecylbenzenesulfonic or
cyclohexanesulfonic acid, dodecanesulfinic, benzenesulfinic or
naphthalenesulfinic acid, butylphosphonic acid, phenylphosphonic
acid, monomethyl or monoethyl phenylphosphonate, monobutyl
benzylphosphonate, dibutylphosphinic acid or diphenylphosphinic
acid.
[0321] If L is an enolate anion, it is preferably an anion of a
.beta.-dicarbonyl compound or of an o-acylphenol. Examples of
.beta.-dicarbonyl compounds are acetylacetone, benzoylacetone,
dibenzoylmethane, ethyl acetoacetate, butyl acetoacetate, lauryl
acetoacetate or .alpha.-acetylcyclohexanone. Examples of
o-acylphenols are 2-acetylphenol, 2-butyroylphenol,
2-acetyl-1-naphthol, 2-benzoylphenol or salicylaldehyde. The
enolate is preferably the anion of a .beta.-dicarbonyl compound
having 5 to 20 carbon atoms.
[0322] Organic salts of zinc or magnesium are preferably an
acetylacetonate or an aliphatic monocarboxylate having, for
example, 1 to 24 carbon atoms. Magnesium acetate, laurate and
stearate, zinc formate, acetate, oenanthate, laurate and stearate
as well as zinc acetylacetonate and magnesium acetylacetonate are
some of the particular preferred examples.
[0323] Zinc stearate, magnesium stearate, zinc acetylacetonate,
magnesium acetylacetonate, zinc acetate and magnesium acetate are
of special interest.
[0324] The inorganic salt of zinc or magnesium is for example a
carbonate containing compound such as
[0325] Zn-hydroxide-carbonate, Mg-hydroxide-carbonate, dolomite,
e.g a Ca/Mg carbonate such as Microdol Super (RTM) from Micro
Minerals (RTM); or
[0326] a natural or synthetic hydrotalcite.
[0327] The natural hydrotalcite is held to possess a structure
Mg.sub.6Al.sub.2(OH).sub.16CO.sub.3.4 H.sub.2O. A typical empirical
formula of a synthetic hydrotalcite is
[0328] Al.sub.2Mg.sub.4.35OH.sub.11.36CO.sub.3(1.67) .cndot.x
H.sub.2O.
[0329] Examples of the synthetic product include:
[0330] Mg.sub.0.7Al.sub.0.3(OH).sub.2(CO.sub.3).sub.0.15
.cndot.0.54 H.sub.2O,
[0331] Mg.sub.4.5Al.sub.2(OH).sub.13CO.sub.3 .cndot.3.5 H.sub.2O,
or
[0332] Mg.sub.4.2Al(OH).sub.12.4CO.sub.3.
[0333] Preferred synthetic hydrotalcites are L-55R II (RTM) from
REHEIS (RTM) as well as ZHT-4A (RTM) and DHT-4A (RTM) from Kyowa
Chemical Industry Co (RTM).
[0334] Component (II) can also be a mixture of two different Mg-
and/or Zn- compounds, for example
[0335] a Mg-stearate and hydrotalcite (DHT-4A (RTM)),
[0336] Zn-stearate and hydrotalcite (DHT-4A (RTM)),
[0337] Mg-acetylacetonate and hydrotalcite (DHT-4A (RTM)),
[0338] Mg-oxide and hydrotalcite (DHT-4A (RTM)),
[0339] Mg-hydroxide and hydrotalcite (DHT-4A (RTM)),
[0340] Zn-hydroxide-carbonate and Mg-stearate,
[0341] Zn-hydroxide-carbonate and Zn-stearate,
[0342] Zn-hydroxide-carbonate and Mg-acetylacetonate,
[0343] Zn-hydroxide-carbonate and Mg-oxide,
[0344] Zn-hydroxide-carbonate and Zn-oxide,
[0345] Zn-hydroxide-carbonate and Mg-hydroxide,
[0346] hydrotalcite (REHEIS (RTM)) and Mg-stearate,
[0347] hydrotalcite (REHEIS (RTM)) and Zn-stearate,
[0348] a hydrotalcite (REHEIS (RTM)) and Mg-oxide,
[0349] dolomite (Microdol Super (RTM)) and Zn-stearate,
[0350] dolomite (Microdol Super (RTM)) and Mg-stearate,
[0351] dolomite (Microdol Super (RTM)) and Zn-oxide,
[0352] dolomite (Microdol Super (RTM)) and Mg-hydroxide,
[0353] Mg-stearate and Zn-stearate,
[0354] Mg-stearate and Zn-acetylacetonate,
[0355] Mg-stearate and Mg-oxide,
[0356] Mg-stearate and Zn-oxide,
[0357] Mg-stearate and Mg-hydroxide,
[0358] Zn-stearate and Mg-acetate,
[0359] Zn-stearate and Mg-oxide,
[0360] Zn-stearate and Mg-hydroxide,
[0361] Mg-acetylacetonate and Zn-acetylacetonate,
[0362] Mg-acetylacetonate and Mg-oxide,
[0363] Mg-acetylacetonate and Zn-oxide,
[0364] Mg-acetylacetonate and Mg-hydroxide,
[0365] Zn-acetylacetonate and Mg-oxide,
[0366] Zn-acetylacetonate and Zn-oxide, or
[0367] Mg-oxide and Zn-oxide.
[0368] In this case, the two different compounds of component (II)
may be present in a weight ratio of 1:10 to 10:1.
[0369] A preferred embodiment of this invention relates to a
stabilizer mixture wherein the compound(s) of component (II) is
(are) selected from the group consisting of Mg carboxylates, Zn
carboxylates, Mg oxides, Zn oxides, Mg hydroxides, Zn hydroxides,
Mg carbonates and Zn carbonates.
[0370] Another preferred embodiment of this invention relates to a
stabilizer mixture wherein component (II) is a Mg carboxylate, a Zn
carboxylate, a hydrotalcite, or a mixture of a Mg carboxylate and a
hydrotalcite.
[0371] A particularly preferred embodiment of this invention
relates to a stabilizer mixture wherein component (II) is Mg
stearate, Zn stearate, a hydrotalcite, in particular DHT-4A (RTM),
or a mixture of Mg stearate and a hydrotalcite.
[0372] Preferred examples of stabilizer mixtures according to the
present invention are:
[0373] 1. TINUVIN 622 (RTM)+CHIMASSORB 944 (RTM)+Mg stearate
[0374] 2. TINUVIN 622 (RTM)+CHIMASSORB 119 (RTM)+Mg stearate
[0375] 3. TINUVIN 622 (RTM)+CHIMASSORB 2020 (RTM)+Mg stearate
[0376] 4. TINUVIN 622 (RTM)+CYASORB UV 3346 (RTM)+Mg stearate
[0377] 5. TINUVIN 622 (RTM)+CYASORB UV 3529 (RTM)+Mg stearate
[0378] 6. TINUVIN 622 (RTM)+UVASORB HA 88 (RTM)+Mg stearate
[0379] 7. TINUVIN 622 (RTM)+UVINUL 5050 H (RTM)+Mg stearate
[0380] 8. TINUVIN 622 (RTM)+ADK STAB LA 63 (RTM)+Mg stearate
[0381] 9. TINUVIN 622 (RTM)+ADK STAB LA 68 (RTM)+Mg stearate
[0382] 10.TINUVIN 622 (RTM)+UVASIL 299 HM (RTM)+Mg stearate
[0383] 11.TINUVIN 622 (RTM)+TINUVIN 770 (RTM)+Mg stearate
[0384] 12.TINUVIN 622 (RTM)+TINUVIN 765 (RTM)+Mg stearate
[0385] 13.TINUVIN 622 (RTM)+TINUVIN 123 (RTM)+Mg stearate
[0386] 14.TINUVIN 622 (RTM)+HOSTAVIN N 20 (RTM)+Mg stearate
[0387] 15.TINUVIN 622 (RTM)+ADK STAB LA 52 (RTM)+Mg stearate
[0388] 16.TINUVIN 622 (RTM)+ADK STAB LA 57 (RTM)+Mg stearate
[0389] 17.TINUVIN 622 (RTM)+CYASORB UV 3581 (RTM)+Mg stearate
[0390] 18.TINUVIN 622 (RTM)+CYASORB UV 3641 (RTM)+Mg stearate
[0391] 19.TINUVIN 622 (RTM)+UVINUL 4050 H (RTM)+Mg stearate
[0392] 20.TINUVIN 622 (RTM)+DASTIB 845 (RTM)+Mg stearate
[0393] 21.TINUVIN 770 (RTM)+CHIMASSORB 944 (RTM)+Mg stearate
[0394] 22.TINUVIN 770 (RTM)+CHIMASSORB 119 (RTM)+Mg stearate
[0395] 23.TINUVIN 770 (RTM)+CHIMASSORB 2020 (RTM)+Mg stearate
[0396] 24.TINUVIN 770 (RTM)+CYASORB UV 3346 (RTM)+Mg stearate
[0397] 25.TINUVIN 770 (RTM)+CYASORB UV 3529 (RTM)+Mg stearate
[0398] 26.TINUVIN 770 (RTM)+UVASORB HA 88 (RTM)+Mg stearate
[0399] 27.TINUVIN 770 (RTM)+UVINUL 5050 H (RTM)+Mg stearate
[0400] 28.TINUVIN 770 (RTM)+ADK STAB LA 63 (RTM)+Mg stearate
[0401] 29.TINUVIN 770 (RTM)+ADK STAB LA 68 (RTM)+Mg stearate
[0402] 30.TINUVIN 770 (RTM)+UVASIL 299 HM (RTM)+Mg stearate
[0403] 31.TINUVIN 770 (RTM)+TINUVIN 765 (RTM)+Mg stearate
[0404] 32.TINUVIN 770 (RTM)+TINUVIN 123 (RTM)+Mg stearate
[0405] 33.TINUVIN 770 (RTM)+HOSTAVIN N 20 (RTM)+Mg stearate
[0406] 34.TINUVIN 770 (RTM)+ADK STAB LA 52 (RTM)+Mg stearate
[0407] 35.TINUVIN 770 (RTM)+ADK STAB LA 57 (RTM)+Mg stearate
[0408] 36.TINUVIN 770 (RTM)+CYASORB UV 3581 (RTM)+Mg stearate
[0409] 37.TINUVIN 770 (RTM)+CYASORB UV 3641 (RTM)+Mg stearate
[0410] 38.TINUVIN 770 (RTM)+UVINUL 4050 H (RTM)+Mg stearate
[0411] 39.TINUVIN 770 (RTM)+DASTIB 845 (RTM)+Mg stearate
[0412] 40.CHIMASSORB 944 (RTM)+CHIMASSORB 119 (RTM)+Mg stearate
[0413] 41.CHIMASSORB 944 (RTM)+CHIMASSORB 2020 (RTM)+Mg
stearate
[0414] 42.CHIMASSORB 944 (RTM)+CYASORB UV 3346 (RTM)+Mg
stearate
[0415] 43.CHIMASSORB 944 (RTM)+CYASORB UV 3529 (RTM)+Mg
stearate
[0416] 44.CHIMASSORB 944 (RTM)+UVASORB HA 88 (RTM)+Mg stearate
[0417] 45.CHIMASSORB 944 (RTM)+UVINUL 5050 H (RTM)+Mg stearate
[0418] 46.CHIMASSORB 944 (RTM)+ADK STAB LA 63 (RTM)+Mg stearate
[0419] 47.CHIMASSORB 944 (RTM)+ADK STAB LA 68 (RTM)+Mg stearate
[0420] 48.CHIMASSORB 944 (RTM)+UVASIL 299 HM (RTM)+Mg stearate
[0421] 49.CHIMASSORB 944 (RTM)+TINUVIN 765 (RTM)+Mg stearate
[0422] 50.CHIMASSORB 944 (RTM)+TINUVIN 123 (RTM)+Mg stearate
[0423] 51.CHIMASSORB 944 (RTM)+HOSTAVIN N 20 (RTM)+Mg stearate
[0424] 52.CHIMASSORB 944 (RTM)+ADK STAB LA 52 (RTM)+Mg stearate
[0425] 53.CHIMASSORB 944 (RTM)+ADK STAB LA 57 (RTM)+Mg stearate
[0426] 54.CHIMASSORB 944 (RTM)+CYASORB UV 3581 (RTM)+Mg
stearate
[0427] 55.CHIMASSORB 944 (RTM)+CYASORB UV 3641 (RTM)+Mg
stearate
[0428] 56.CHIMASSORB 944 (RTM)+UVINUL 4050 H (RTM)+Mg stearate
[0429] 57.CHIMASSORB 944 (RTM)+DASTIB 845 (RTM)+Mg stearate
[0430] 58.CHIMASSORB 119 (RTM)+CYASORB UV 3529 (RTM)+Mg
stearate
[0431] 59.CHIMASSORB 119 (RTM)+ADK STAB LA 63 (RTM)+Mg stearate
[0432] 60.CHIMASSORB 119 (RTM)+TINUVIN 765 (RTM)+Mg stearate
[0433] 61.CHIMASSORB 119 (RTM)+TINUVIN 123 (RTM)+Mg stearate
[0434] 62.CHIMASSORB 119 (RTM)+ADK STAB LA 52 (RTM)+Mg stearate
[0435] 63.CHIMASSORB 119 (RTM)+CYASORB UV 3641 (RTM)+Mg
stearate
[0436] The formulations obtained by replacing in the formulations 2
to 63 Mg stearate by Zn stearate are also preferred. Further, the
formulations 1 to 66 wherein Mg stearate is replaced by DHT-4A or
Mg oxide or by combinations of the coadditives listed as component
(II) are preferred.
[0437] Examples of the latter formulations are:
[0438] 1. TINUVIN 622 (RTM)+CHIMASSORB 944 (RTM)+DHT-4A (RTM)+Mg
stearate
[0439] 2. TINUVIN 770 (RTM)+CHIMASSORB 944 (RTM)+DHT-4A (RTM)+Mg
stearate
[0440] 3. TINUVIN 622 (RTM)+CHIMASSORB 119 (RTM)+DHT-4A (RTM)+Mg
stearate
[0441] 4. TINUVIN 770 (RTM)+UVASORB HA 88 (RTM)+DHT-4A (RTM)+Mg
stearate
[0442] 5. TINUVIN 622 (RTM)+UVASORB HA 88 (RTM)+DHT-4A (RTM)+Mg
stearate
[0443] 6. TINUVIN 622 (RTM)+UVASIL 299 (RTM)+DHT-4A (RTM)+Mg
stearate
[0444] 7. TINUVIN 622 (RTM)+CHIMASSORB 2020 (RTM)+DHT-4A (RTM)+Mg
stearate
[0445] 8. TINUVIN 770 (RTM)+CHIMASSORB 2020 (RTM)+DHT-4A (RTM)+Mg
stearate
[0446] The commercial product TINUVIN 622 (RTM) corresponds to the
compound of the formula (B-7-a).
[0447] The commercial product CHIMASSORB 944 (RTM) corresponds to
the compound of the formula (B-1-a) wherein R.sub.6 is
hydrogen.
[0448] The commercial product CHIMASSORB 119 (RTM) corresponds to
the compound of the formula (B-2-a) wherein R.sub.13 is methyl.
[0449] The commercial product CHIMASSORB 2020 (RTM) corresponds to
the compound of the formula (B-1-b) wherein R.sub.6 is
hydrogen.
[0450] The commercial product CYASORB UV 3346 (RTM) corresponds to
the compound of the formula (B-1-d) wherein R.sub.6 is
hydrogen.
[0451] The commercial product CYASORB UV 3529 (RTM) corresponds to
the compound of the formula (B-1-d) wherein R6 is methyl.
[0452] The commercial product UVASORB HA 88 (RTM) corresponds to
the product (B-6-a) wherein R.sub.32 is hydrogen.
[0453] The commercial product UVINUL 5050 H (RTM) corresponds to
the compound of the formula (B-4-a) wherein R.sub.18 is
hydrogen.
[0454] The commercial product ADK STAB LA 63 (RTM) corresponds to
the compound of the formula (B-5-a) wherein R.sub.30 is methyl.
[0455] The commercial product ADK STAB LA 68 (RTM) corresponds to
the compound of the formula (B-5-a) wherein R.sub.30 is
hydrogen.
[0456] The commercial product UVASIL 299 (RTM) corresponds to the
compound of the formula (B-3-a) wherein R.sub.16 is hydrogen.
[0457] The commercial product TINUVIN 770 (RTM) corresponds to the
compound of the formula (A-1-b) wherein E.sub.1 is hydrogen.
[0458] The commercial product TINUVIN 765 (RTM) corresponds to the
compound of the formula (A-1-b) wherein E.sub.1 is methyl.
[0459] The commercial product TINUVIN 123 (RTM) corresponds to the
compound of the formula (A-1-b) wherein E.sub.1 is octyloxy.
[0460] The commercial product HOSTAVIN N 20 (RTM) corresponds to
the compound of the formula (A-3-a) wherein E.sub.12 is
hydrogen.
[0461] The commercial product ADK STAB LA 52 (RTM) corresponds to
the compound of the formula (A-1-d) wherein E.sub.1 is methyl.
[0462] The commercial product ADK STAB LA 57 (RTM) corresponds to
the compound of the formula (A-1-d) wherein E.sub.1 is
hydrogen.
[0463] The commercial product CYASORB UV 3581 (RTM) corresponds to
the compound of the formula (A-6-a) wherein E.sub.18 is
hydrogen.
[0464] The commercial product CYASORB UV 3641 (RTM) corresponds to
the compound of the formula (A-6-a) wherein E.sub.18 is methyl.
[0465] The commercial product UVINUL 4050 H (RTM) corresponds to
the compound of the formula (A-10-a) wherein E.sub.29 is
hydrogen.
[0466] The commercial product DASTIB 845 (RTM) corresponds to the
compound of the formula (A-1-a) wherein E.sub.1 is hydrogen.
[0467] A further preferred embodiment of this invention relates to
a stabilizer mixture containing additionally
[0468] (X-1) a pigment or
[0469] (X-2) an UV absorber or
[0470] (X-3) a pigment and an UV absorber.
[0471] The pigment (component (X-1)) may be an inorganic or organic
pigment.
[0472] Examples of inorganic pigments are titanium dioxide, zinc
oxide, carbon black, cadmium sulfide, cadmium selenide, chromium
oxide, iron oxide, lead oxide and so on.
[0473] Examples of organic pigments are azo pigments,
anthraquinones, phthalocyanines, tetrachloroisoindolinones,
quinacridones, isoindolines, perylenes, pyrrolopyrroles (such as
Pigment Red 254) and so on.
[0474] All pigments described in "Gchter/Muller: Plastics Additives
Handbook, 3rd Edition, Hanser Publishers, Munich Vienna New York",
page 647 to 659, point 11.2.1.1 to 11.2.4.2 can be used as
component (X-1).
[0475] A particularly preferred pigment is titanium dioxide,
optionally in combination with an organic pigment.
[0476] Examples of such organic pigments are:
[0477] C.I. (Colour Index) Pigment Yellow 93, C.I. Pigment Yellow
95, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment
Yellow 155, C.I. Pigment Yellow 162, C.I. Pigment Yellow 168, C.I.
Pigment Yellow 180, C.I. Pigment Yellow 183, C.I. Pigment Red 44,
C.I. Pigment Red 170, C.I. Pigment Red 202, C.I. Pigment Red 214,
C.I. Pigment Red 254, C.I. Pigment Red 264, C.I. Pigment Red 272,
C.I. Pigment Red 48:2, C.I. Pigment Red 48:3, C.I. Pigment Red
53:1, C.I. Pigment Red 57:1, C.I. Pigment Green 7, C.I. Pigment
Blue 15:1, C.I. Pigment Blue 15:3 and C.I. Pigment Violet 19.
[0478] Examples of the UV absorber (component (X-2)) are a
2-(2'-hydroxyphenyl)benzotriazole, a 2-hydroxybenzophenone, an
ester of substituted or unsubstituted benzoic acid, an acrylate, an
oxamide, a 2-(2-hydroxyphenyl)-1,3,5-triazine, a monobenzoate of
resorcinol or a formamidine.
[0479] The 2-(2'-hydroxyphenyl)benzotriazole is e.g.
2-(2'-hydroxy-5'-methylphenyl)-benzotriazole,
2-(3',5'-di-tert-butyl-2'-h- ydroxyphenyl)benzotriazole,
2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazol- e,
2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-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'-- hydroxyphenyl)benzotriazole,
2-(3',5'-bis-(.alpha.,.alpha.-dimethylbenzyl)-
-2'-hydroxyphenyl)benzotriazole, mixture of
2-(3'-tert-butyl-2'-hydroxy-5'- -(2-octyloxycarbonylethyl)
phenyl)-5-chloro-benzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-
-5-chloro-benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonyl- ethyl)
phenyl)-5-chloro-benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-m- ethoxycarbonylethyl)
phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'--
(2-octyloxycarbonylethyl) phenyl)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)phenylbenzotri-
azole, 2,2'-methylene-bis
[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-- ylphenol] or the
transesterification product of 2-[3'-tert-butyl-5'-(2-met-
hoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with
polyethylene glycol 300;
[R-CH.sub.2CH.sub.2--COO(CH.sub.2).sub.3-].sub.2 where
R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl.
[0480]
2-(3',5'-Di-tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chloro-benzotriazole
and 2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole are
preferred.
[0481] The 2-hydroxybenzophenone is for example the 4-hydroxy,
4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy,
4,2',4'-trihydroxy or 2'-hydroxy-4,4'-dimethoxy derivatives.
[0482] 2-Hydroxy-4-octyloxybenzophenone is preferred.
[0483] The ester of a substituted or unsubstituted benzoic acid is
for example 4-tert-butyl-phenyl salicylate, phenyl salicylate,
octylphenyl salicylate, dibenzoyl resorcinol,
bis(4-tert-butylbenzoyl) resorcinol, benzoyl resorcinol,
2,4-di-tertbutylphenyl 3,5-di-tert-butyl-4-hydroxyben- zoate,
hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl
3,5-di-tert-butyl-4-hydroxybenzoate or
2-methyl-4,6-di-tert-butylphenyl
3,5-di-tert-butyl-4-hydroxybenzoate.
[0484] 2,4-Di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate
and hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate are
preferred.
[0485] The acrylate is for example ethyl
.alpha.-cyano-.beta.,.beta.-diphe- nylacrylate, isooctyl
.alpha.-cyano-.beta.,.beta.-diphenylacrylate, methyl
.alpha.-carbomethoxycinnamate, methyl
.alpha.-cyano-.beta.-methyl-p-metho- xycinnamate, butyl
.alpha.-cyano-.beta.-methyl-p-methoxy-cinnamate, methyl
.alpha.-carbomethoxy-p-methoxycinnamate or
N-(.beta.-carbomethoxy-.beta.-- cyanovinyl)-2-methylindoline.
[0486] The oxamide is 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 or its mixture with
2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide or mixtures of ortho-
and para-methoxy-disubstituted oxanilides or mixtures of o- and
p-ethoxy-disubstituted oxanilides.
[0487] The 2-(2-hydroxyphenyl)-1,3,5-triazine is for example
2,4,6-tris(2-hydroxy-4-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-hydroxy-4-propyl-oxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazi-
ne,
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)
phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,
2-[4-(dodecyloxy/tridecylox-
y-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-tr-
iazine,
2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-
-dimethylphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphen- yl-1,3,5-triazine,
2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazi- ne,
2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)
phenyl]-1,3,5-triazine or
2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-pheny-
l-1,3,5-triazine.
[0488]
2-(2-Hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-tr-
iazine and 2-(2-hydroxy-4-hexyloxy)
phenyl-4,6-diphenyl-1,3,5-triazine are preferred.
[0489] The monobenzoate of resorcinol is for example the compound
of the formula 80
[0490] The formamidine is for example the compound of the formula
81
[0491] The UV absorber is in particular a
2-(2'-hydroxyphenyl)benzotriazol- e, a 2-hydroxybenzophenone or a
hydroxyphenyltriazine.
[0492] A further preferred embodiment of this invention relates to
a stabilizer mixture which additionally contains as a further
component (XX) an organic salt of Ca, an inorganic salt of Ca, Ca
oxide or Ca hydroxide.
[0493] Examples of an organic salt of Ca are Ca-stearate,
Ca-laurate, Ca-lactate and Ca-stearoyl-lactate.
[0494] Examples of an inorganic salt of Ca are CaCO.sub.3,
CaCl.sub.2, CaF.sub.2, Ca.sub.3(PO.sub.4).sub.2, CaHPO.sub.4,
Ca(PO.sub.3).sub.2, Ca.sub.2P.sub.2O.sub.7, CaSO.sub.4 and
CaSio.sub.3.
[0495] Further preferred examples of stabilizer mixtures according
to the present invention are:
[0496] a. TINUVIN 622 (RTM)+CHIMASSORB 944 (RTM)+Mg stearate+Ca
stearate
[0497] b. TINUVIN 770 (RTM)+CHIMASSORB 944 (RTM)+Mg stearate+Ca
stearate
[0498] c. TINUVIN 622 (RTM)+CHIMASSORB 119 (RTM)+Mg stearate+Ca
stearate
[0499] d. TINUVIN 770 (RTM)+UVASORB HA 88 (RTM)+Mg stearate+Ca
stearate
[0500] e. TINUVIN 622 (RTM)+UVASORB HA 88 (RTM)+Mg stearate+Ca
stearate
[0501] f. TINUVIN 622 (RTM)+UVASIL 299 (RTM)+Mg stearate+Ca
stearate
[0502] g. TINUVIN 622 (RTM)+CHIMASSORB 2020 (RTM)+Mg stearate+Ca
stearate
[0503] h. TINUVIN 770 (RTM)+CHIMASSORB 2020 (RTM)+Mg stearate+Ca
stearate
[0504] i. TINUVIN 622 (RTM)+CHIMASSORB 944 (RTM)+DHT-4A (RTM)+Ca
stearate
[0505] j. TINUVIN 770 (RTM)+CHIMASSORB 944 (RTM)+DHT-4A (RTM)+Ca
stearate
[0506] k. TINUVIN 622 (RTM)+CHIMASSORB 119 (RTM)+DHT-4A (RTM)+Ca
stearate
[0507] l. TINUVIN 770 (RTM)+UVASORB HA 88 (RTM)+DHT-4A (RTM)+Ca
stearate
[0508] m. TINUVIN 622 (RTM)+UVASORB HA 88 (RTM)+DHT-4A (RTM)+Ca
stearate
[0509] n. TINUVIN 622 (RTM)+UVASIL 299 (RTM)+DHT-4A (RTM)+Ca
stearate
[0510] o. TINUVIN 622 (RTM)+CHIMASSORB 2020 (RTM)+DHT-4A (RTM)+Ca
stearate
[0511] p. TINUVIN 770 (RTM)+CHIMASSORB 2020 (RTM)+DHT-4A (RTM)+Ca
stearate
[0512] The stabilizer mixture according to this invention is
suitable for stabilizing organic materials against degradation
induced by light, heat or oxidation. Examples of such organic
materials are the following:
[0513] 1. Polymers of monoolefins and diolefins, for example
polypropylene, polyisobutylene, polybut-1-ene,
poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as
polymers of cycloolefins, for instance of cyclopentene or
norbornene, polyethylene (which optionally can be crosslinked), for
example high density polyethylene (HDPE), high density and high
molecular weight polyethylene (HDPE-HMW), high density and
ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density
polyethylene (MDPE), low density polyethylene (LDPE), linear low
density polyethylene (LLDPE), (VLDPE) and (ULDPE), or polyvinyl
cyclohexane.
[0514] Polyolefins, i.e. the polymers of monoolefins exemplified in
the preceding paragraph, preferably polyethylene and polypropylene,
can be prepared by different, and especially by the following,
methods:
[0515] a) radical polymerisation (normally under high pressure and
at elevated temperature).
[0516] b) catalytic polymerisation using a catalyst that normally
contains one or more than one metal of groups IVb, Vb, VIb or VIII
of the Periodic Table. These metals usually have one or more than
one ligand, typically oxides, halides, alcoholates, esters, ethers,
amines, alkyls, alkenyls and/or aryls that may be either .pi.- or
.sigma.-coordinated. These metal complexes may be in the free form
or fixed on substrates, typically on activated magnesium chloride,
titanium(III) chloride, alumina or silicon oxide. These catalysts
may be soluble or insoluble in the polymerisation medium. The
catalysts can be used by themselves in the polymerisation or
further activators may be used, typically metal alkyls, metal
hydrides, metal alkyl halides, metal alkyl oxides or metal
alkyloxanes, said metals being elements of groups Ia, IIa and/or
IIIa of the Periodic Table. The activators may be modified
conveniently with further ester, ether, amine or silyl ether
groups. These catalyst systems are usually termed Phillips,
Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene
or single site catalysts (SSC).
[0517] 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).
[0518] 3. Copolymers of monoolefins and diolefins with each other
or with other vinyl monomers, for example ethylene/propylene
copolymers, linear low density polyethylene (LLDPE) and mixtures
thereof with low density polyethylene (LDPE), propylene/but-1-ene
copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene
copolymers, ethylene/hexene copolymers, ethylene/methylpentene
copolymers, ethylene/heptene copolymers, ethylene/octene
copolymers, propylene/butadiene copolymers, isobutylene/isoprene
copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl
methacrylate copolymers, ethylene/vinyl acetate copolymers and
their copolymers with carbon monoxide or ethylene/acrylic acid
copolymers and their salts (ionomers) as well as terpolymers of
ethylene with propylene and a diene such as hexadiene,
dicyclopentadiene or ethylidene-norbornene; and mixtures of such
copolymers with one another and with polymers mentioned in 1)
above, for example polypropylene/ethylene-propylene copolymers,
LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic
acid copolymers (EAA), LLDPE/EVA, LLDPE/EM and alternating or
random polyalkylene/carbon monoxide copolymers and mixtures thereof
with other polymers, for example polyamides.
[0519] 4. Hydrocarbon resins (for example C.sub.5-C.sub.9)
including hydrogenated modifications thereof (e.g. tackifiers) and
mixtures of polyalkylenes and starch.
[0520] 5. Polystyrene, poly(p-methylstyrene),
poly(.alpha.-methylstyrene).
[0521] 6. Copolymers of styrene or .alpha.-methylstyrene with
dienes or acrylic derivatives, for example styrene/butadiene,
styrene/acrylonitrile, styrene/alkyl methacrylate,
styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl
methacrylate, styrene/maleic anhydride,
styrene/acrylonitrile/methyl acrylate; mixtures of high impact
strength of styrene copolymers and another polymer, for example a
polyacrylate, a diene polymer or an ethylene/propylene/diene
terpolymer; and block copolymers of styrene such as
styrene/butadiene/styrene, styrene/isoprene/styrene,
styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/
styrene.
[0522] 7. Graft copolymers of styrene or .alpha.-methylstyrene, for
example styrene on polybutadiene, styrene on polybutadiene-styrene
or polybutadiene-acrylonitrile copolymers; styrene and
acrylonitrile (or methacrylonitrile) on polybutadiene; styrene,
acrylonitrile and methyl methacrylate on polybutadiene; styrene and
maleic anhydride on polybutadiene; styrene, acrylonitrile and
maleic anhydride or maleimide on polybutadiene; styrene and
maleimide on polybutadiene; styrene and alkyl acrylates or
methacrylates on polybutadiene; styrene and acrylonitrile on
ethylene/propylene/diene terpolymers; styrene and acrylonitrile on
polyalkyl acrylates or polyalkyl methacrylates, styrene and
acrylonitrile on acrylate/butadiene copolymers, as well as mixtures
thereof with the copolymers listed under 6), for example the
copolymer mixtures known as ABS, MBS, ASA or AES polymers.
[0523] 8. Halogen-containing polymers such as polychloroprene,
chlorinated rubbers, 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 copolymers.
[0524] 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.
[0525] 10. Copolymers of the monomers mentioned under 9) with each
other or with other unsaturated monomers, for example
acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl acrylate
copolymers, acrylonitrile/alkoxyalkyl acrylate or
acrylonitrilevinyl halide copolymers or acrylonitrile/ alkyl
methacrylate/butadiene terpolymers.
[0526] 11. Polymers derived from unsaturated alcohols and amines or
the acyl derivatives or acetals thereof, for example polyvinyl
alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate,
polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or
polyallyl melamine; as well as their copolymers with olefins
mentioned in 1) above.
[0527] 12. Homopolymers and copolymers of cyclic ethers such as
polyalkylene glycols, polyethylene oxide, polypropylene oxide or
copolymers thereof with bisglycidyl ethers.
[0528] 13. Polyacetals such as polyoxymethylene and those
polyoxymethylenes which contain ethylene oxide as a comonomer;
polyacetals modified with thermoplastic polyurethanes, acrylates or
MBS.
[0529] 14. Polyphenylene oxides and sulfides, and mixtures of
polyphenylene oxides with styrene polymers or polyamides.
[0530] 15. Polyurethanes derived from hydroxyl-terminated
polyethers, polyesters or polybutadienes on the one hand and
aliphatic or aromatic polyisocyanates on the other, as well as
precursors thereof.
[0531] 16. Polyamides and copolyamides derived from diamines and
dicarboxylic acids and/or from aminocarboxylic acids or the
corresponding lactams, for example polyamide 4, polyamide 6,
polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide
12, aromatic polyamides starting from m-xylene diamine and adipic
acid; polyamides prepared from hexamethylenediamine and isophthalic
or/and terephthalic acid and with or without an elastomer as
modifier, for example poly-2,4,4,-trimethylhexame- thylene
terephthalamide or poly-m-phenylene isophthalamide; and also block
copolymers of the aforementioned polyamides with polyolefins,
olefin copolymers, ionomers or chemically bonded or grafted
elastomers; or with polyethers, e.g. with polyethylene glycol,
polypropylene glycol or polytetramethylene glycol; as well as
polyamides or copolyamides modified with EPDM or ABS; and
polyamides condensed during processing (RIM polyamide systems).
[0532] 17. Polyureas, polyimides, polyamide-imides, polyetherimids,
polyesterimids, polyhydantoins and polybenzimidazoles.
[0533] 18. Polyesters derived from dicarboxylic acids and diols
and/or from hydroxycarboxylic acids or the corresponding lactones,
for example polyethylene terephthalate, polybutylene terephthalate,
poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene
naphthalate (PAN) and polyhydroxybenzoates, as well as block
copolyether esters derived from hydroxyl-terminated polyethers; and
also polyesters modified with polycarbonates or MBS.
[0534] 19. Polycarbonates and polyester carbonates.
[0535] 20. Polysulfones, polyether sulfones and polyether
ketones.
[0536] 21. Crosslinked polymers derived from aldehydes on the one
hand and phenols, ureas and melamines on the other hand, such as
phenol/formaldehyde resins, urea/formaldehyde resins and
melamine/formaldehyde resins.
[0537] 22. Drying and non-drying alkyd resins.
[0538] 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.
[0539] 24. Crosslinkable acrylic resins derived from substituted
acrylates, for example epoxy acrylates, urethane acrylates or
polyester acrylates.
[0540] 25. Alkyd resins, polyester resins and acrylate resins
crosslinked with melamine resins, urea resins, isocyanates,
isocyanurates, polyisocyanates or epoxy resins.
[0541] 26. Crosslinked epoxy resins derived from aliphatic,
cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g.
products of diglycidyl ethers of bisphenol A and bisphenol F, which
are crosslinked with customary hardeners such as anhydrides or
amines, with or without accelerators.
[0542] 27. Natural polymers such as cellulose, rubber, gelatin and
chemically modified homologous derivatives thereof, for example
cellulose acetates, cellulose propionates and cellulose butyrates,
or the cellulose ethers such as methyl cellulose; as well as rosins
and their derivatives.
[0543] 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, POM/MBS,
PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO,
PBT/PC/ABS or PBT/PET/PC.
[0544] 29. Naturally occurring and synthetic organic materials
which are pure monomeric compounds or mixtures of such compounds,
for example mineral oils, animal and vegetable fats, oil and waxes,
or oils, fats and waxes based on synthetic esters (e.g. phthalates,
adipates, phosphates or trimellitates) and also mixtures of
synthetic esters with mineral oils in any weight ratios, typically
those used as spinning compositions, as well as aqueous emulsions
of such materials.
[0545] 30. Aqueous emulsions of natural or synthetic rubber, e.g.
natural latex or latices of carboxylated styrene/butadiene
copolymers.
[0546] This invention therefore additionally relates to a
composition comprising an organic material subject to degradation
induced by light, heat or oxidation and the stabilizer mixture
described above.
[0547] The compositions according to the present invention
preferably do not contain a mineral oil.
[0548] Further, the organic material is preferably different from
polyethylene, when component (I) is the combination of the
compounds (B-1-a-1) and (B-7-a), in particular the combination of a
compound of the class (.beta.-1) and a compound of the class
(.beta.-7); and, at the same time, component (II) is Zn
carboxylate, in particular an organic salt of Zn.
[0549] A preferred embodiment of the present invention relates to
polypropylene containing a compound of the formula (B-1), a
compound of the formula (B-7) and a Zn-carboxylate; 82
[0550] in which
[0551] R.sub.1, R.sub.3, R.sub.4 and R.sub.5 independently of one
another are hydrogen, C.sub.1-C.sub.12alkyl,
C.sub.5-C.sub.12cycloalkyl, C.sub.1-C.sub.4-alkyl-substituted
C.sub.5-C.sub.12cycloalkyl, phenyl, phenyl which is substituted by
--OH and/or C.sub.1-C.sub.10alkyl; C.sub.7-C.sub.9phenylalkyl,
C.sub.7-C.sub.9phenylalkyl which is substituted on the phenyl
radical by --OH and/or C.sub.1-C.sub.10alkyl; or a group of the
formula (b-I) 83
[0552] R.sub.2 is C.sub.2-C.sub.18alkylene,
C.sub.5-C.sub.7cycloalkylene or
C.sub.1-C.sub.4alkylenedi(B.sub.5-C.sub.7cycloalkylene), or
[0553] the radicals R.sub.1, R.sub.2 and R.sub.3, together with the
nitrogen atoms to which they are bonded, perform a 5- to
10-membered heterocyclic ring, or R.sub.4 and R.sub.5, together
with the nitrogen atom to which they are bonded, form a 5- to
10-membered heterocyclic ring,
[0554] R.sub.6 is hydrogen, C.sub.1-C.sub.8alkyl, O.sup.-, --OH,
--CH.sub.2CN, C.sub.1-C.sub.18alkoxy, C.sub.5-C.sub.12cycloalkoxy,
C.sub.3-C.sub.6alkenyl, C.sub.7-C.sub.9phenylalkyl unsubstituted or
substituted on the phenyl by 1, 2 or 3 C.sub.1-C.sub.4alkyl; or
[0555] C.sub.1-C.sub.8acyl, and
[0556] b.sub.1 is a number from 2 to 50,
[0557] with the proviso that at least one of the radicals R.sub.1,
R.sub.3, R.sub.4 and R.sub.5 is a group of the formula (b-I);
84
[0558] wherein A.sub.1 is hydrogen or C.sub.1-C.sub.4alkyl,
[0559] A.sub.2 is a direct bond or C.sub.1-C.sub.10alkylene,
and
[0560] n.sub.1 is a number from 2 to 50.
[0561] Another embodiment of the present invention is a method for
stabilizing an organic material against degradation induced by
light, heat or oxidation, which comprises incorporating into the
organic material the stabilizer mixture described above.
[0562] The organic material is preferably a synthetic polymer, in
particular from one of the above groups. Polyolefins are preferred
and polyethylene, polypropylene, a polyethylene copolymer or a
polypropylene copolymer are particularly preferred.
[0563] The components (I), (II) and optionally (X-1) and/or (X-2),
as well as optionally component (XX) may be added to the organic
material to be stabilized either individually or mixed with one
another.
[0564] The total amount of the two different sterically hindered
amine compounds (component (I)) in the organic material to be
stabilized is preferably 0.005 to 5%, in particular 0.01 to 1% or
0.05 to 1%, relative to the weight of the organic material.
[0565] The Mg and/or Zn compounds (component (II)) are present in
the organic material in a total amount of preferably 0.005 to 1%,
in particular 0.05 to 0.2%, relative to the weight of the organic
material.
[0566] The pigment (component (X-1)) is optionally present in the
organic material in an amount of preferably 0.01 to 10%, in
particular 0.05 to 1%, relative to the weight of the organic
material.
[0567] The UV absorber (component (X-2)) is optionally present in
the organic material in an amount of preferably 0.01 to 1%, in
particular 0.05 to 0.5%, relative to the weight of the organic
material.
[0568] The total amount of component (X-3) (the pigment in
combination with the UV absorber) is preferably 0.01 to 10%,
relative to the weight of the organic material. The weight ratio of
the UV absorber to the pigment is for example 2:1 to 1:10.
[0569] When the pigment used is titanium dioxide in combination
with an organic pigment as described above, titanium dioxide is
preferably present in the organic material in an amount of 0.01 to
5%, relative to the weight of the organic material, and the organic
pigment may be present in an amount of, for example, 0.01 to 2%,
relative to the weight of the organic material.
[0570] The Ca compound (component (XX)) is optionally present in
the organic material in an amount of e.g. 0.005 to 1%, preferably
0.05 to 0.2%.
[0571] The weight ratio of the two different sterically hindered
amine compounds forming component (I) is for example 1:10 to 10:1,
preferably 1:5to5:1, in particular 1:2to2:1.
[0572] The weight ratio of the components (I):(II) is for example
1:10 to 20:1, preferably 1:5 to 5:1, in particular 1:2 to 2:1.
[0573] The weight ratio of the components (I):(X-1) is for example
1:10 to 10:1, preferably 1:5 to 5:1, in particular 1:2 to 2:1.
[0574] The weight ratio of the components (I):(X-2) is for example
1:5 to 5:1, preferably 1:2 to 2:1.
[0575] The weight ratio of the components (I):(X-3) is for example
1:10 to 10:1, preferably 1:5 to 5:1, in particular 1:2 to 2:1.
[0576] The weight ratio of the components (I):(XX) is for example
1:10 to 10:1, preferably 1:5 to 5:1, in particular 1:2 to 2:1.
[0577] The above components can be incorporated into the organic
material to be stabilized by known methods, for example before or
during shaping or by applying the dissolved or dispersed compounds
to the organic material, if necessary with subsequent evaporation
of the solvent. The components can be added to the organic material
in the form of a powder, granules or a masterbatch, which contains
these components in, for example, a concentration of from 2.5 to
25% by weight.
[0578] If desired, the components (I), (II) and optionally (X-1)
and/or (X-2), as well as component (XX) can be melt blended with
each other before incorporation in the organic material. They can
be added to a polymer before or during the polymerization or before
the crosslinking.
[0579] The materials stabilized according to this invention can be
used in a wide variety of forms, for example as films, fibres,
tapes, moulding compositions, profiles or as binders for paints,
adhesives or putties.
[0580] Examples of processing or transformation of the plastics
according to the present invention are:
[0581] Injection blow molding, extrusion, blow molding,
rotomolding, in mold decoration (back injection), slush molding,
injection molding, co-injection molding, forming, compression
molding, pressing, film extrusion (cast film; blown film), fiber
spinning (woven, non-woven), drawing (uniaxial, biaxial),
annealing, deep drawing, calandering, mechanical transformation,
sintering, coextrusion, coating, lamination, crosslinking
(radiation, peroxide, silane), vapor deposition, weld together,
glue, vulkanization, thermoforming, pipe extrusion, profile
extrusion, sheet extrusion; sheet casting, spin coating, strapping,
foaming, recycling/rework, extrusion coating, visbreaking
(peroxide, thermal), fiber melt blown, spun bonded, surface
treatment (corona discharge, flame, plasma), sterilization (by
gamma rays, electron beams), cast polymerization (R&M process,
RAM extrusion), gel-coating, tape extrusion, GMT-process,
SMC-process, plastisol, and dipping (PVC, latex).
[0582] The plastics according to the present invention may be used
for the preparation of:
[0583] I-1) Floating devices, marine applications, pontoons, buoys,
plastic lumber for decks, piers, boats, kayaks, oars, and beach
reinforcements.
[0584] I-2) Automotive applications, in particular bumpers,
dashboards, battery, rear and front linings, moldings parts under
the hood, hat shelf, trunk linings, interior linings, air bag
covers, electronic moldings for fittings (lights), panes for
dashboards, headlamp glass, instrument panel, exterior linings,
upholstery, automotive lights, head lights, parking lights, rear
lights, stop lights, interior and exterior trims; door panels; gas
tank; glazing front side; rear windows; seat backing, exterior
panels, wire insulation, profile extrusion for sealing, cladding,
pillar covers, chassis parts, exhaust systems, fuel filter/filler,
fuel pumps, fuel tank, body side mouldings, convertible tops,
exterior mirrors, exterior trim, fasteners/fixings, front end
module, glass, hinges, lock systems, luggage/roof racks,
pressed/stamped parts, seals, side impact protection, sound
deadener/insulator and sunroof.
[0585] I-3) Road traffic devices, in particular sign postings,
posts for road marking, car accessories, warning triangles, medical
cases, helmets, tires.
[0586] I-4) Devices for plane, railway, motor car (car, motorbike)
including furnishings.
[0587] I-5) Devices for space applications, in particular rockets
and satellites, e.g. reentry shields.
[0588] I-6) Devices for architecture and design, mining
applications, acoustic quietized systems, street refuges, and
shelters.
[0589] II-1) Appliances, cases and coverings in general and
electric/electronic devices (personal computer, telephone, handy,
printer, television-sets, audio and video devices), flower pots,
satellite TV bowl, and panel devices.
[0590] II-2) Jacketing for other materials such as steel or
textiles.
[0591] II-3) Devices for the electronic industry, in particular
insulation for plugs, especially computer plugs, cases for electric
and electronic parts, printed boards, and materials for electronic
data storage such as chips, check cards or credit cards.
[0592] II-4) Electric appliances, in particular washing machines,
tumblers, ovens (microwave oven), dish-washers, mixers, and
irons.
[0593] II-5) Covers for lights (e.g. street-lights,
lamp-shades).
[0594] II-6) Applications in wire and cable (semi-conductor,
insulation and cable-jacketing).
[0595] II-7) Foils for condensers, refrigerators, heating devices,
air conditioners, encapsulating of electronics, semi-conductors,
coffee machines, and vacuum cleaners.
[0596] III-1) Technical articles such as cogwheel (gear), slide
fittings, spacers, screws, bolts, handles, and knobs.
[0597] III-2) Rotor blades, ventilators and windmill vanes, solar
devices, swimming pools, swimming pool covers, pool liners, pond
liners, closets, wardrobes, dividing walls, slat walls, folding
walls, roofs, shutters (e.g. roller shutters), fittings,
connections between pipes, sleeves, and conveyor belts.
[0598] III-3) Sanitary articles, in particular shower cubicles,
lavatory seats, covers, and sinks.
[0599] III-4) Hygienic articles, in particular diapers (babies,
adult incontinence), feminine hygiene articles, shower curtains,
brushes, mats, tubs, mobile toilets, tooth brushes, and bed
pans.
[0600] III-5) Pipes (cross-linked or not) for water, waste water
and chemicals, pipes for wire and cable protection, pipes for gas,
oil and sewage, guttering, down pipes, and drainage systems.
[0601] III-6) Profiles of any geometry (window panes) and
siding.
[0602] III-7) Glass substitutes, in particular extruded plates,
glazing for buildings (monolithic, twin or multiwall), aircraft,
schools, extruded sheets, window film for architectural glazing,
train, transportation, sanitary articles, and greenhouse.
[0603] III-8) Plates (walls, cutting board), extrusion-coating
(photographic paper, tetrapack and pipe coating), silos, wood
substitute, plastic lumber, wood composites, walls, surfaces,
furniture, decorative foil, floor coverings (interior and exterior
applications), flooring, duck boards, and tiles.
[0604] III-9) Intake and outlet manifolds.
[0605] III-10) Cement-, concrete-, composite-applications and
covers, siding and cladding, hand rails, banisters, kitchen work
tops, roofing, roofing sheets, tiles, and tarpaulins.
[0606] IV-1) Plates (walls and cutting board), trays, artificial
grass, astroturf, artificial covering for stadium rings
(athletics), artificial floor for stadium rings (athletics), and
tapes.
[0607] IV-2) Woven fabrics continuous and staple, fibers
(carpets/hygienic articles/geotextiles/monofilaments; filters;
wipes/curtains (shades)/medical applications), bulk fibers
(applications such as gown/protection clothes), nets, ropes,
cables, strings, cords, threads, safety seat-belts, clothes,
underwear, gloves; boots; rubber boots, intimate apparel, garments,
swimwear, sportswear, umbrellas (parasol, sunshade), parachutes,
paraglides, sails, "balloon-silk", camping articles, tents,
airbeds, sun beds, bulk bags, and bags.
[0608] IV-3) Membranes, insulation, covers and seals for roofs,
tunnels, dumps, ponds, dumps, walls roofing membranes,
geomembranes, swimming pools, curtains (shades)/sun-shields,
awnings, canopies, wallpaper, food packing and wrapping (flexible
and solid), medical packaging (flexible & solid),
airbags/safety belts, arm- and head rests, carpets, centre console,
dashboard, cockpits, door, overhead console module, door trim,
headliners, interior lighting, interior mirrors, parcel shelf, rear
luggage cover, seats, steering column, steering wheel, textiles,
and trunk trim.
[0609] V) Films (packaging, dump, laminating, agriculture and
horticulture, greenhouse, mulch, tunnel, silage), bale wrap,
swimming pools, waste bags, wallpaper, stretch film, raffia,
desalination film, batteries, and connectors.
[0610] VI-1) Food packing and wrapping (flexible and solid), BOPP,
BOPET, bottles.
[0611] VI-2) Storage systems such as boxes (crates), luggage,
chest, household boxes, pallets, shelves, tracks, screw boxes,
packs, and cans.
[0612] VI-3) Cartridges, syringes, medical applications, containers
for any transportation, waste baskets and waste bins, waste bags,
bins, dust bins, bin liners, wheely bins, container in general,
tanks for water/used water/chemistry/gas/oil/gasoline/diesel; tank
liners, boxes, crates, battery cases, troughs, medical devices such
as piston, ophthalmic applications, diagnostic devices, and packing
for pharmaceuticals blister.
[0613] VII-1) Extrusion coating (photo paper, tetrapack, pipe
coating), household articles of any kind (e.g. appliances, thermos
bottle/clothes hanger), fastening systems such as plugs, wire and
cable clamps, zippers, closures, locks, and snap-closures.
[0614] VII-2) Support devices, articles for the leisure time such
as sports and fitness devices, gymnastics mats, ski-boots,
inline-skates, skis, big foot, athletic surfaces (e.g. tennis
grounds); screw tops, tops and stoppers for bottles, and cans.
[0615] VII-3) Furniture in general, foamed articles (cushions,
impact absorbers), foams, sponges, dish clothes, mats, garden
chairs, stadium seats, tables, couches, toys, building kits
(boards/figures/balls), playhouses, slides, and play vehicles.
[0616] VI -4) Materials for optical and magnetic data storage.
[0617] VII-5) Kitchen ware (eating, drinking, cooking,
storing).
[0618] VII-6) Boxes for CD's, cassettes and video tapes; DVD
electronic articles, office supplies of any kind (ball-point pens,
stamps and ink-pads, mouse, shelves, tracks), bottles of any volume
and content (drinks, detergents, cosmetics including perfumes), and
adhesive tapes.
[0619] VII-7) Footwear (shoes/shoe-soles), insoles, spats,
adhesives, structural adhesives, food boxes (fruit, vegetables,
meat, fish), synthetic paper, labels for bottles, couches,
artificial joints (human), printing plates (flexographic), printed
circuit boards, and display technologies.
[0620] VII-8) Devices of filled polymers (talc, chalk, china clay
(kaolin), wollastonite, pigments, carbon black, TiO.sub.2, mica,
nanocomposites, dolomite, silicates, glass, asbestos).
[0621] The stabilized material may additionally also contain
various conventional additives, for example:
[0622] 1. Antioxidants
[0623] 1.1. Alkylated monophenols, for example
2,6-di-tert-butyl-4-methylp- henol,
2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethyl phenol,
2,6-di-tert-butyl-4-n-butyl-phenol,
2,6-di-tert-butyl-4-isobutylphenol,
2,6-dicyclopentyl-4-methylphenol,
2-(.alpha.-methylcyclohexyl)-4,6-dimeth- ylphenol,
2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,
2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are
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-dimethyl-6-(1'-methylhep- tadec-1'-yl) phenol,
2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures
thereof.
[0624] 1.2. Alkylthiomethylphenols, for example
2,4-dioctylthiomethyl-6-te- rt-butylphenol,
2,4-dioctylthiomethyl-6-methylphenol,
2,4-dioctylthiomethyl-6-ethylphenol,
2,6-didodecylthiomethyl-4-nonylpheno- l.
[0625] 1.3. Hydroquinones and alkylated hydroquinones, for example
2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone,
2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol,
2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole,
3,5-di-tert-butyl-4-hydroxyanisole,
3,5-di-tert-butyl-4-hydroxyphenyl stearate,
bis-(3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
[0626] 1.4. Tocopherols, for example .alpha.-tocopherol,
.beta.-tocopherol, .gamma.-tocopherol, .delta.-tocopherol and
mixtures thereof (Vitamin E).
[0627] 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.
[0628] 1.6. Alkylidenebisphenols, for example
2,2'-methylenebis(6-tert-but- yl-4-methylphenol),
2,2'-methylenebis(6-tert-butyl-4-ethylphenol),
2,2'-methylenebis[4-methyl-6-(.alpha.-methylcyclohexyl) phenol],
2,2'-methylenebis(4-methyl-6-cyclohexylphenol),
2,2'-methylenebis(6-nonyl- -4-methylphenol),
2,2'-methylenebis(4,6-di-tert-butylphenol),
2,2'-ethylidenebis(4,6-di-tert-butylphenol),
2,2'-ethylidenebis(6-tert-bu- tyl-4-isobutylphenol),
2,2'-methylenebis[6-(.alpha.-methylbenzyl)-4-nonylp- henol],
2,2'-methylenebis [6-(.alpha.,.alpha.-dimethylbenzyl)-4-nonylpheno-
l], 4,4'-methylenebis(2,6-di-tert-butylphenol),
4,4'-methylenebis(6-tert-b- utyl-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-dimethyl-2-hydroxyphenyl) butane,
2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane,
2,2-bis-(5-tert-butyl-4-hydroxy
2-methylphenyl)-4-n-dodecylmercaptobutane- ,
1,1,5,5-tetra-(5-tert-butyl-4-hydroxy 2-methylphenyl)pentane.
[0629] 1.7. O--, N--and S-benzyl compounds, for example
3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydibenzyl ether,
octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate,
tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate,
tris(3,5-di-tert-butyl-4-hydroxybenzyl) amine,
bis(4-tert-butyl-3-hydroxy-
-2,6-dimethylbenzyl)dithioterephthalate,
bis(3,5-di-tert-butyl-4-hydroxybe- nzyl)sulfide,
isooctyl-3,5di-tert-butyl-4-hydroxybenzylmercaptoacetate.
[0630] 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)
malonate,
bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-but-
yl-4-hydroxybenzyl) malonate.
[0631] 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(35-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,
2,4,6-tis(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
[0632] 1.10. Triazine Compounds, for example
2,4-bis(octylmercapto)-6-(3,5-
-di-tert-butyl-4-hydroxyanilino)-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-triazine,
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-4-hydroxyphenylethyl)-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-dicyclohexyl-4-hydroxybenzyl)isocyanurate.
[0633] 1.11. Benzylphosphonates, for example
dimethyl-2,5-di-tert-butyl-4-- hydroxybenzylphosphonate,
diethyl-3,5-di-tert-butyl-4-hydroxybenzylphospho- nate,
dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
dioctadecyl-5-tert-butyl-4-hydroxy3-methylbenzylphosphonate, the
calcium salt of the monoethyl ester of
3,5-di-tert-butyl-4-hydroxybenzylphosphoni- c acid.
[0634] 1.12. Acylaminophenols, for example 4-hydroxylauranilide,
4-hydroxystearanilide, octyl
N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbama- te.
[0635] 1.13. Esters of
.beta.-(3,5-di-tert-butyl-4-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,
trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo
[2.2.2]octane.
[0636] 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]octane.
[0637] 1.15. Esters of
.beta.-(3,5-dicyclohexyl-4-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) isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo
[2.2.2]octane.
[0638] 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) isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo
[2.2.2]octane.
[0639] 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)hexamethyl-
enediamine, N,N'-bis
(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethyl- enediamine,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine.
[0640] 1.18. Ascorbic acid (vitamin C)
[0641] 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-phenyl- enediamine,
N-isopropyl-N'-phenyl-p-phenylenediamine,
N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine,
N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine,
N-cyclohexyl-N'-phenyl-p- -phenylenediamine,
4-(p-toluenesulfamoyl)diphenylamine,
N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine,
N-allyldiphenylamine, 4-isopropoxydiphenylamine,
N-phenyl-1-naphthylamine- , 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-nonanoylamino-phenol,
4-dodecanoylaminophenol, 4-octadecanoylaminophenol,
bis(4-methoxyphenyl)amine,
2,6-di-tert-butyl-4-dimethylaminomethylphenol,
2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,
N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane,
1,2-bis[(2-methylphenyl) amino]ethane, 1,2-bis(phenylamino)propane,
(o-tolyl)biguanide, Bis[4-(1',3'-dimethylbutyl)phenyl]amine,
tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and
dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono-
and dialkylated nonyldiphenylamines, a mixture of mono- and
dialkylated dodecyldiphenylamines, a mixture of mono- and
dialkylated isopropylvisohexyldiphenylamines, 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-phenothiazines- , N-allylphenothiazin,
N,N,N',N'-tetraphenyl-1,4-diamino-but-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-tetramethylpiperidi- n-4-one,
2,2,6,6-tetramethylpiperidin-4-ol.
[0642] 2. UV absorbers and light stabilisers
[0643] 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.
[0644] 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.
[0645] 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-dibenz [d,g]-
1,3,2-dioxaphosphocin,
6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-diben- z
[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)
methylphosphite,
bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite.
[0646] 5. Hydroxylamines, for example, N,N-dibenzylhydroxylamine,
N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine,
N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine,
N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine,
N-hexadecyl-N-octadecylhydroxylamine,
N-heptadecyl-N-octadecylhydroxylami- ne, N,N-dialkylhydroxylamine
derived from hydrogenated tallow amine.
[0647] 6. Nitrones, for example, N-benzyl-alpha-phenyl-nitrone,
N-ethyl-alpha-methyl-nitrone, N-octyl-alpha-heptyl-nitrone,
N-lauryl-alpha-undecyl-nitrone,
N-tetradecyl-alpha-tridecyl-nitrone,
N-hexadecyl-alpha-pentadecyl-nitrone,
N-octadecyl-alpha-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-dialkylhydroxylamine derived from hydrogenated tallow
amine.
[0648] 7. Thiosynergists, for example, dilauryl thiodipropionate or
distearyl thiodipropionate.
[0649] 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 dibutyldithiocarbamate,
dioctadecyl disulfide, pentaerythritol
tetrakis(.beta.-dodecylmercapto)propionate.
[0650] 9. 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 tin
pyrocatecholate.
[0651] 10. 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").
[0652] 11. 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.
[0653] 12. Other additives, for example, plasticisers, lubricants,
emulsifiers, pigments, rheology additives, catalysts, flow-control
agents, optical brighteners, flameproofing agents, antistatic
agents and blowing agents.
[0654] 13. Benzofuranones and indolinones, for example those
disclosed in U.S. Pat. No. 4,325,863, U.S. Pat. No. 4,338,244, U.S.
Pat. No. 5,175,312, U.S. Pat. No. 5,216,052, U.S. Pat. No.
5,252,643, DE-A-4316611, DE-A-4316622, DE-A-4316876, EP-A-0589839
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)-5,7-di-tert-butyl-benzofuran-2-one,
3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one.
[0655] The weight ratio of the total amount of components (I), (II)
and optionally (X-1) and/or (X-2), as well as optionally component
(XX) to the total amount of the conventional additives can be, for
example, 100:1 to 1:100.
[0656] The examples below illustrate the invention in greater
detail. All percentages and parts are by weight, unless stated
otherwise.
[0657] Stabilizers used in the following Examples I to IV:
[0658] (For the polymeric compounds, the mean degree of
polymerization is indicated in each case.)
Compound (B-1-a-1)
[0659] (CHIMASSORB 944 (RTM)) 85
[0660] with b.sub.1 being 4.5.
Compound (B-2-a-1)
[0661] (CHIMASSORB 119 (RTM)) 86
Compound (B-7-a-1)
[0662] (TINUVIN 622 (RTM)) 87
[0663] with n.sub.1 being 5.1.
Compound (X-2-a)
[0664] TINUVIN 327 (RTM) 88
Example I
Light Stabilization of Polypropylene Tapes
[0665] 100 parts of polypropylene powder (melt flow index: 3.2 g/10
min at 230.degree. C. and 2160 g) are blended in a barrel mixer
with 0.05 parts of pentaerythrityl
tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 0.05
parts of tris[2,4-di-tert-butylphenyl] phosphite and the stabilizer
system indicated in Table 1. Then, the blend is compounded in an
extruder at temperatures of 180.degree.-220.degree. C. The granules
obtained on extrusion and granulation are transformed into films at
220.degree.-260.degree. C. in a second extruder equipped with a
flat sheet die. The films are cut into ribbons which are drawn to
achieve a stretch ratio of 1:6. The tapes obtained with this
procedure are finally 50 .mu.m thick and 2.5 mm wide.
[0666] The tapes are mounted without tension on sample holders and
exposed to natural weathering in Florida (45.degree. South, direct,
approximately 145 kLy/year). Periodically, the tensile strength of
the exposed tapes is measured. The received energy (in kLy)
corresponding to a loss of 50% (E.sub.50) of the initial tensile
strength or the % retained tensile strength after 320 kLy is a
measure for the stabilizing efficiency of the stabilizer
system.
[0667] The values obtained are summarized in Table 1.
1TABLE 1 E.sub.50 (kLy) to 50% retained tensile strength or %
retained tensile Stabilizer System strength after 320 kLy 0.1% of
Mg stearate 58 0.05% of (B-1-a-1) + 0.05% of (B-7-a-1) + 0.1% 78%
of Mg stearate
Example II
Light Stabilization of Polypropylene Homopolymer Films
[0668] 100 parts of unstabilized polypropylene powder (melt flow
index: 3.8 g/10 min at 230.degree. C. and 2160 g) are homogenized
at 200.degree. C. for 10 min in a Brabender plastograph with 0.05
parts of
pentaerythrityl-tetrakis{3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)-
, 0.10 parts of tris{2,4-di-tert-butylphenyl} phosphite and the
stabilizer system indicated in Tables 2a, 2b, 2c and 2d. The
material thus obtained is compression molded in a laboratory press
between two aluminum foils for 6 min at 260.degree. C. to a 0.5 mm
thick film which is cooled immediately to room temperature in a
water-cooled press. Samples of 60 mm.times.25 mm are cut out of
these 0.5 mm films and are exposed in a WEATHER-OMETER Ci 65 (black
panel temperature 63.+-.2.degree. C., without water-spraying).
[0669] Periodically, these samples are removed from the exposure
apparatus and their carbonyl content is measured with an infrared
spectrophotometer. The exposure time corresponding to formation of
a carbonyl absorbance of 0.1 in hours (T.sub.0.1) is a measure for
the efficiency of the stabilizer system. The values obtained are
summarized in Tables 2a, 2b, 2c and 2d.
2TABLE 2a T.sub.0.1 in hours to 0.1 Stabilizer system carbonyl
absorbance 0.1% of Mg stearate + 0.1% of (X-2-a) 360 0.025% of
(B-1-a-1) + 0.025% of (B-7-a-1) + 0.1% 1960 of Mg stearate + 0.1%
of (X-2-a) 0.025% of (B-2-a-1) + 0.025% of (B-7-a-1) + 0.1% 1820 of
Mg stearate + 0.1% of (X-2-a)
[0670]
3TABLE 2b T.sub.0.1 in hours to 0.1 Stabilizer system carbonyl
absorbance 0.1% of Zn stearate + 0.5% of TiO.sub.2 (rutile) 430
0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 0.1% 1540 of Zn
stearate + 0.5% of TiO.sub.2 (rutile) 0.025% of (B-2-a-1) + 0.025%
of (B-7-a-1) + 0.1% 1840 of Zn stearate + 0.5% of TiO.sub.2
(rutile)
[0671]
4 TABLE 2c T.sub.0.1 in hours to 0.1 Stabilizer system carbonyl
absorbance 0.025% of (B-1-a-1) + 0.025% of 2020 (B-7-a-1) + 0.1% of
hydrotalcite (DHT-4A (RTM)) + 0.5% of TiO.sub.2 (rutile)
[0672]
5TABLE 2d T.sub.0.1 in hours to 0.1 Stabilizer system carbonyl
absorbance 0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 0.1% 2320 of
hydrotalcite (DHT-4A (RTM)) + 0.1% of (X-2-a)
Example III
Light Stabilization of Polypropylene Copolymer Films
[0673] 100 parts of unstabilized copolypropylene powder (melt flow
index: 6 g/10 min at 230.degree. C. and 2160 g; 10% ethylene
monomer) are homogenized at 200.degree. C. for 10 min in a
Brabender plastograph with 0.05 parts of
pentaerythrityl-tetrakis{3-(3,5-di-tert-butyl-4-hydroxyphen- yl)
propionate}, 0.10 parts of tris{2,4-di-tert-butylphenyl} phosphite
and the stabilizer system indicated in Table 3. The material thus
obtained is compression molded in a laboratory press between two
aluminum foils for 6 min at 260.degree. C. to a 0.5 mm thick film
which is cooled immediately to room temperature in a water-cooled
press. Samples of 60 mm.times.25 mm are cut out of these 0.5 mm
films and are exposed in a WEATHER-OMETER Ci 65 (black panel
temperature 63.+-.2.degree. C., without water-spraying).
[0674] Periodically, these samples are removed from the exposure
apparatus and their carbonyl content is measured with an infrared
spectrophotometer. The exposure time corresponding to formation of
a carbonyl absorbance of 0.1 is a measure for the efficiency of the
stabilizer system. The values obtained are summarized in Table
3.
6TABLE 3 T.sub.0.1 in hours to 0.1 Stabilizer system carbonyl
absorbance 0.1% of hydrotalcite (DHT-4A (RTM)) + 0.5% of 390
TiO.sub.2 (rutile) 0.05% of (B-1-a-1) + 0.05% of 4000 (B-7-a-1) +
0.1% of hydrotalcite (DHT-4A (RTM)) + 0.5% of TiO.sub.2 (rutile)
0.05% of (B-2-a-1) + 0.05% of 4960 (B-7-a-1) + 0.1% of hydrotalcite
(DHT-4A (RTM)) + 0.5% of TiO.sub.2 (rutile)
Example IV
Light Stabilization of Polyethylene HD Films
[0675] 100 parts of unstabilized high density polyethylene powder
(density: 0.964 g cm.sup.-3, melt flow index: 5.0 g/10 min at
190.degree. C. and 2160 g) are homogenized at 180.degree. C. for 10
min in a Brabender plastograph with 0.03 parts of octadecyl
3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and the stabilizer
system indicated in Tables 4a, 4b, 4c, 4d, 4e, 4f, 4g, 4h and 4i.
The material thus obtained is compression molded in a laboratory
press between two aluminum foils for 6 min at 210.degree. C. to a
0.5 mm thick film which is cooled immediately to room temperature
in a water-cooled press. Samples of 60 mm.times.25 mm are cut out
of these 0.5 mm films and are exposed in a WEATHER-OMETER Ci 65
(black panel temperature 63.+-.2.degree. C., without
water-spraying).
[0676] Periodically, these samples are removed from the exposure
apparatus and their carbonyl content is measured with an infrared
spectrophotometer. The exposure time corresponding to formation of
a carbonyl absorbance of 0.1 is a measure for the efficiency of the
stabilizer mixture. The values obtained are summarized in Table 4a,
4b, 4c, 4d, 4e, 4f, 4g, 4h and 4i.
7TABLE 4a T.sub.0.1 in hours to 0.1 Stabilizer system carbonyl
absorbance 0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 0.1% 18060
of Mg stearate
[0677]
8TABLE 4b T.sub.0.1 in hours to 0.1 Stabilizer system carbonyl
absorbance 0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 0.1% 18055
of hydrotalcite (DHT-4A (RTM))
[0678]
9TABLE 4c T.sub.0.1 in hours to 0.1 Stabilizer system carbonyl
absorbance 0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 22210 0.05%
of Mg stearate + 0.05% of Ca stearate
[0679]
10TABLE 4d T.sub.0.1 in hours to 0.1 Stabilizer system carbonyl
absorbance 0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 15680 0.05%
of hydrotalcite (DHT-4A (RTM)) + 0.1% of Ca stearate
[0680]
11TABLE 4e T.sub.0.1 in hours to 0.1 Stabilizer system carbonyl
absorbance 0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 23040 0.05%
of hydrotalcite (DHT-4A (RTM)) + 0.1% of Mg stearate
[0681]
12TABLE 4f T.sub.0.1 in hours to 0.1 Stabilizer system carbonyl
absorbance 0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 0.1%
>28700 of Mg stearate + 0.5% of TiO.sub.2 (rutile)
[0682]
13TABLE 4g T.sub.0.1 in hours to 0.1 carbonyl Stabilizer system
absorbance 0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 0.05%
>28700 of Mg stearate + 0.5% of TiO.sub.2 (rutile) + 0.05% of Ca
stearate
[0683]
14TABLE 4h T.sub.0.1 in hours to 0.1 carbonyl Stabilizer system
absorbance 0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 0.05%
>28700 of hydrotalcite (DHT-4A (RTM)) + 0.5% of TiO.sub.2
(rutile) + 0.05% of Ca stearate
[0684]
15TABLE 4i T.sub.0.1 in hours to 0.1 carbonyl Stabilizer system
absorbance 0.025% of (B-1-a-1) + 0.025% of (B-7-a-1) + 0.05%
>28700 of hydrotalcite (DHT-4A (RTM)) + 0.5% of TiO.sub.2
(rutile) + 0.05% of Mg stearate
* * * * *