U.S. patent application number 10/179693 was filed with the patent office on 2003-04-17 for imidazolidinone derivatives.
Invention is credited to Lazzari, Dario, Zagnoni, Graziano.
Application Number | 20030073835 10/179693 |
Document ID | / |
Family ID | 8184066 |
Filed Date | 2003-04-17 |
United States Patent
Application |
20030073835 |
Kind Code |
A1 |
Lazzari, Dario ; et
al. |
April 17, 2003 |
Imidazolidinone derivatives
Abstract
A compound of the formula (IA) or (IB) 1 wherein G.sub.1,
G.sub.2, G.sub.3 and G.sub.4 are independently of one another
C.sub.1-C.sub.18alkyl or C.sub.5-C.sub.12cycloalkyl or the radicals
G.sub.1 and G.sub.2 and the radicals G.sub.3 and G.sub.4 form
independently of one another, together with the carbon atom they
are attached to, C.sub.5-C.sub.12cycloalkyl; R is hydrogen
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18hydroxyalkyl,
C.sub.2-C.sub.18alkenyl, C.sub.5-C.sub.12cycloalkyl,
C.sub.7-C.sub.12phenylalkyl unsubstituted or substituted on the
phenyl radical by C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy; or C.sub.1-C.sub.18alkanoyl; R* is hydrogen,
C.sub.1-C.sub.18alkyl, oxyl, --OH, --CH.sub.2CN,
C.sub.3-C.sub.6alkenyl, C.sub.3-C.sub.8alkynyl,
C.sub.7-C.sub.12phenylalk- yl unsubstituted or substituted on the
phenyl radical by C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy; C.sub.1-C.sub.8acyl, C.sub.1-C.sub.18alkoxy,
C.sub.1-C.sub.18hydroxyalkoxy, C.sub.2-C.sub.18alkenyloxy,
C.sub.5-C.sub.12cycloalkoxy, C.sub.7-C.sub.12phenylalkoxy
unsubstituted or substituted on the phenyl radical by
C.sub.1-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy;
C.sub.1-C.sub.18alkanoyloxy, (C.sub.1-C.sub.18alkoxy)carbonyl,
glycidyl or a group --CH.sub.2CH(OH)(G) with G being hydrogen,
methyl or phenyl; n is 1, 2, 3 or 4; n* is 1, 2 or 3; X is an
organic radical of a valency equal to n; and X* is a triazinic
radical with a valency equal to n*; with the proviso that when n is
1, R is methyl, ethyl, propyl, C.sub.1-C.sub.18hydroxyalkyl,
C.sub.2-C.sub.18alkenyl, C.sub.5-C.sub.12cycloalkyl or
C.sub.1-C.sub.18alkanoyl. The compounds described above are useful
for stabilizing an organic material against degradation induced by
light, heat or oxidation.
Inventors: |
Lazzari, Dario; (Bologna,
IT) ; Zagnoni, Graziano; (Vergato, IT) |
Correspondence
Address: |
JoAnn Villamizar
Ciba Specialty Chemicals Corporation
540 White Plains Road
P.O. Box 2005
Tarrytown
NY
10591-9005
US
|
Family ID: |
8184066 |
Appl. No.: |
10/179693 |
Filed: |
June 24, 2002 |
Current U.S.
Class: |
544/212 |
Current CPC
Class: |
C08K 5/34926 20130101;
C08K 5/3445 20130101; C07D 233/32 20130101; C07D 403/04 20130101;
C07D 403/14 20130101 |
Class at
Publication: |
544/212 |
International
Class: |
C07D 43/14 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 31, 2001 |
EP |
01810751.6 |
Claims
1. A compound of the formula (IA) or (IB) 46wherein G.sub.1,
G.sub.2, G.sub.3 and G.sub.4 are independently of one another
C.sub.1-C.sub.18alkyl or C.sub.5-C.sub.12cycloalkyl or the radicals
G.sub.1 and G.sub.2 and the radicals G.sub.3 and G.sub.4 form
independently of one another, together with the carbon atom they
are attached to, C.sub.5-C.sub.12cycloalkyl; R is
C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18hydroxyalkyl,
C.sub.2-C.sub.18alkenyl, C.sub.5-C.sub.12cycloalkyl,
C.sub.7-C.sub.12phenylalkyl unsubstituted or substituted on the
phenyl radical by C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy; or C.sub.1-C.sub.18alkanoyl; R* is hydrogen,
C.sub.1-C.sub.18alkyl, oxyl, --OH, --CH.sub.2CN,
C.sub.3-C.sub.6alkenyl, C.sub.3-C.sub.8alkynyl,
C.sub.7-C.sub.12phenylalkyl unsubstituted or substituted on the
phenyl radical by C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy; C.sub.1-C.sub.8acyl, C.sub.1-C.sub.18alkoxy,
C.sub.1-C.sub.18hydroxyalkoxy, C.sub.2-C.sub.18alkenyloxy,
C.sub.5-C.sub.12cycloalkoxy, C.sub.7-C.sub.12phenylalkoxy
unsubstituted or substituted on the phenyl radical by
C.sub.1-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy;
C.sub.1-C.sub.18alkanoyloxy, (C.sub.1-C.sub.18alkoxy)carbonyl,
glycidyl or a group, --CH.sub.2CH(OH)(G) with G being hydrogen,
methyl or phenyl; n is 1, 2, 3 or 4; n* is 1, 2 or 3; X is an
organic radical of a valency equal to n; when n* is 1, X* is a
group of the formula (IB-1) 47wherein Z.sub.1* and Z.sub.2* are
independently of one another --O-- or >N--R.sub.3*; R.sub.1*,
R.sub.2* and R.sub.3* are independently of one another hydrogen,
C.sub.1-C.sub.18alkyl, C.sub.3-C.sub.18alkenyl,
C.sub.5-C.sub.12cycloalkyl which is unsubstituted or substituted by
C.sub.1-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy; or
C.sub.7-C.sub.9phenylalkyl which is unsubstituted or substituted on
the phenyl radical by C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy; when n* is 2, X* is a group of the formula
(IB-2) 48wherein Z.sub.1* and R.sub.1* are as defined above; when
n* is 3, X* is a group of the formula (IB-3); 49when n is 2, 3 or
4, each of the radicals G.sub.1, G.sub.2, G.sub.3, G.sub.4 and R
can have the same or a different meaning in the units of the
formula 50when n* is 2 or 3, each of the radicals G.sub.1, G.sub.2,
G.sub.3, G.sub.4 and R* can have the same or a different meaning in
the units of the formula 51with the proviso that when n is 1, R is
methyl, ethyl, propyl, C.sub.1-C.sub.18hydroxyalkyl,
C.sub.2-C.sub.18alkenyl, C.sub.5-C.sub.12cycloalkyl or
C.sub.1-C.sub.18alkanoyl.
2. A compound of the formula (IA) according to claim 1 wherein when
n is 1, X is C.sub.2-C.sub.18alkyl, C.sub.2-C.sub.18hydroxyalkyl,
C.sub.2-C.sub.18alkyl interrupted by oxygen, sulphur or
>N--R.sub.0 with R.sub.0 being as defined below;
C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18alkynyl,
C.sub.5-C.sub.12cycloalkyl unsubstituted or substituted by --OH,
C.sub.1-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy; phenyl or
C.sub.7-C.sub.9phenylalkyl unsubstituted or substituted on the
phenyl radical by --OH, C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy; or X is one of the groups of the formulae
(II-a) to (II-m) 52Y.sub.1, Y.sub.2, Y.sub.5, Y.sub.6, Y.sub.7 and
Y.sub.9 are a direct bond, C.sub.1-C.sub.12alkylene,
C.sub.5-C.sub.12cycloalkylene or phenylene; Y.sub.3, Y.sub.4,
Y.sub.8, Y.sub.10, Y.sub.11 and Y.sub.12 are
C.sub.2-C.sub.12alkylene, C.sub.5-C.sub.12cycloalkylene or
phenylene; R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7 and R.sub.13 are hydrogen, C.sub.1-C.sub.18alkyl,
C.sub.2-C.sub.18alkyl interrupted by oxygen, sulphur or
>N--R.sub.0 with R.sub.0 being as defined below;
C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18alkynyl,
C.sub.5-C.sub.12cycloalkyl unsubstituted or substituted by
C.sub.1-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy; phenyl
unsubstituted or substituted by C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy; or C.sub.7-C.sub.9phenylalkyl unsubstituted
or substituted on the phenyl radical by C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy; Z.sub.1, Z.sub.2 and Z.sub.3 are
independently of one another --O-- or >N--R.sub.16; R.sub.0,
R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.14, R.sub.15
and R.sub.16 are independently of one another hydrogen,
C.sub.1-C.sub.18alkyl, C.sub.3-C.sub.18alkenyl,
C.sub.5-C.sub.12cycloalkyl which is unsubstituted or substituted by
C.sub.1-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy; or
C.sub.7-C.sub.9phenylalkyl which is unsubstituted or substituted on
the phenyl radical by C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy; with the proviso that the formula (II-b) is
different from ethoxycarbonyl; when n is 2, X is
C.sub.2-C.sub.12alkylene, C.sub.2-C.sub.16alkylene interrupted by
oxygen, sulphur or >N--R.sub.0' with R.sub.0' being as defined
below; C.sub.2-C.sub.12alkenylene, C.sub.2-C.sub.12alkynylene,
C.sub.5-C.sub.12cycloalkylene,
C.sub.5-C.sub.12cycloalkylene-(C.sub.1-C.s-
ub.4alkylene)-C.sub.5-C.sub.12cycloalkylene,
C.sub.1-C.sub.4alkylene-(C.su-
b.5-C.sub.12cycloalkylene)-C.sub.1-C.sub.4alkylene, phenylene,
phenylene-(C.sub.1-C.sub.4alkylene)-phenylene or
C.sub.1-C.sub.4alkylene-- phenylene-C.sub.1-C.sub.4alkylene, or X
is one of the groups of the formulae (III-a) to (III-j) 53Y.sub.1',
Y.sub.1", Y.sub.2', Y.sub.2", Y.sub.5', Y.sub.5", Y.sub.6',
Y.sub.6", Y.sub.7' and Y.sub.7" are independently of one another a
direct bond, C.sub.1-C.sub.12alkylene,
C.sub.5-C.sub.12cycloalkylene or phenylene; Y.sub.3', Y.sub.3",
Y.sub.4', Y.sub.4", Y.sub.8', Y.sub.8", Y.sub.11', Y.sub.11",
Y.sub.12' and Y.sub.12" are independently of one another
C.sub.2-C.sub.12alkylene, C.sub.5-C.sub.12cycloalkylene or
phenylene; A.sub.1, A.sub.2, A.sub.3, A.sub.4, A.sub.5, A.sub.6,
A.sub.7, A.sub.8 and A.sub.9 are C.sub.2-C.sub.12alkylene,
C.sub.2-C.sub.12alkylene interrupted by oxygen, sulphur or
>N--R.sub.0' with R.sub.0' being as defined below,
C.sub.2-C.sub.12alkenylene, C.sub.2-C.sub.12alkynylene,
C.sub.5-C.sub.12cycloalkylene,
C.sub.5-C.sub.12cycloalkylene-(C.sub.1-C.s-
ub.4alkylene)-C.sub.5-C.sub.12cycloalkylene,
C.sub.1-C.sub.4alkylene-(C.su-
b.5-C.sub.12cycloalkylene)-C.sub.1-C.sub.4alkylene, phenylene,
phenylene-(C.sub.1-C.sub.4alkylene)-phenylene or
C.sub.1-C.sub.4alkylene-- phenylene-C.sub.1-C.sub.4alkylene; and
A.sub.1 and A.sub.5 are additionally a direct bond; Z.sub.1',
Z.sub.2' and Z.sub.3' are independently of one another --O-- or
>N--R.sub.16'; and R.sub.0', R.sub.14' and R.sub.16' are
independently of one another hydrogen, C.sub.1-C.sub.18alkyl,
C.sub.3-C.sub.18alkenyl, C.sub.5-C.sub.12cycloalky- l which is
unsubstituted or substituted by C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy; or C.sub.7-C.sub.9phenylalkyl which is
unsubstituted or substituted on the phenyl radical by
C.sub.1-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy: when n is 3, X
is C.sub.5-C.sub.25alkantriyl, C.sub.4-C.sub.18triacyl or a group
of the formula (IV); 54Y.sub.13', Y.sub.13" and Y.sub.13'" are
independently of one another C.sub.2-C.sub.12alkylene,
C.sub.5-C.sub.12cycloalkylene or phenylene; Z.sub.1", Z.sub.2" and
Z.sub.3" are independently of one another --O-- or
>N--R.sub.16"; and R.sub.16" is hydrogen, C.sub.1-C.sub.1,alkyl,
C.sub.3-C.sub.18alkenyl, C.sub.5-C.sub.12cycloalky- l which is
unsubstituted or substituted by C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy; or C.sub.7-C.sub.9phenylalkyl which is
unsubstituted or substituted on the phenyl radical by
C.sub.1-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy; and when n is 4,
X is C.sub.5-C.sub.20alkantetrayl, C.sub.6-C.sub.22tetraacyl or a
group of the formula (V) 55Y.sub.14' and Y.sub.14" are
independently of one another C.sub.2-C.sub.12alkylene,
C.sub.5-C.sub.12cycloalkylene or phenylene; Z.sub.1'", Z.sub.2'", M
and T are independently of one another --O-- or >N--R.sub.16'",
and M and T are additionally --S--; R.sub.16'" is hydrogen,
C.sub.1-C.sub.18alkyl, C.sub.3-C.sub.18alkenyl,
C.sub.5-C.sub.12cycloalkyl which is unsubstituted or substituted by
C.sub.1-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy; or
C.sub.7-C.sub.9phenylalkyl which is unsubstituted or substituted on
the phenyl radical by C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy; and q is an integer from 2 to 12.
3. A compound according to claim 1 wherein G.sub.1, G.sub.2,
G.sub.3 and G.sub.4 are methyl.
4. A compound of the formula (IA) according to claim 1 wherein R is
C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.12hydroxyalkyl,
C.sub.2-C.sub.8alkenyl or C.sub.5-C.sub.8cycloalkyl.
5. A compound of the formula (IA) according to claim 1 wherein R is
propyl, C.sub.1-C.sub.12hydroxyalkyl, C.sub.2-C.sub.8alkenyl or
C.sub.5-C.sub.8cycloalkyl.
6. A compound of the formula (IB) according to claim 1 wherein R*
is hydrogen, C.sub.1-C.sub.4alkyl, oxyl, --OH,
C.sub.3-C.sub.6alkenyl, benzyl, C.sub.1-C.sub.8acyl,
C.sub.1-C.sub.12alkoxy, C.sub.1-C.sub.12hydroxyalkoxy,
C.sub.2-C.sub.8alkenyloxy or C.sub.5-C.sub.8cycloalkoxy.
7. A compound of the formula (IA) according to claim 1 wherein R is
methyl, propyl, butyl, octyl, hydroxybutyl, 2-propenyl or
cyclohexyl.
8. A compound of the formula (IB) according to claim 1 wherein R*
is hydrogen, methyl, allyl, acetyl, methoxy, propoxy, butoxy,
octyloxy, hydroxybutoxy, 2-propenyloxy or cyclohexyloxy.
9. A compound of the formula (IA) according to claim 1 wherein n is
2.
10. A compound according to claim 2 wherein when n is 1, X is
C.sub.2-C.sub.12alkyl, C.sub.2-C.sub.12hydroxyalkyl,
C.sub.2-C.sub.12alkyl interrupted by oxygen or >N--R.sub.0 with
R.sub.0 being as defined below; C.sub.2-C.sub.18alkenyl,
C.sub.5-C.sub.8cycloalkyl unsubstituted or substituted by
C.sub.1-C.sub.4alkyl; or benzyl unsubstituted or substituted on the
phenyl radical by --OH and/or C.sub.1-C.sub.4alkyl; or X is one of
the groups of the formulae (II-a) to (II-m); Y.sub.1, Y.sub.2,
Y.sub.5, Y.sub.6, Y.sub.7 and Y.sub.9 are a direct bond,
C.sub.1-C.sub.6alkylene, cyclohexylene or phenylene; Y.sub.3,
Y.sub.4, Y.sub.8, Y.sub.10, Y.sub.11, and Y.sub.12 are
C.sub.2-C.sub.6alkylene, cyclohexylene or phenylene; R.sub.1,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7 and R.sub.13
are hydrogen, C.sub.1-C.sub.12alkyl, C.sub.2-C.sub.12alkyl
interrupted by oxygen or >N--R.sub.0 with R.sub.0 being as
defined below; C.sub.2-C.sub.18alkenyl, C.sub.5-C.sub.8cycloalkyl
unsubstituted or substituted by C.sub.1-C.sub.4alkyl; phenyl
unsubstituted or substituted by C.sub.1-C.sub.4alkyl; or benzyl
unsubstituted or substituted on the phenyl radical by
C.sub.1-C.sub.4alkyl; Z.sub.1, Z.sub.2 and Z.sub.3 are
independently of one another --O-- or >N--R.sub.16; R.sub.0,
R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12, R.sub.14, R.sub.15
and R.sub.16 are independently of one another hydrogen,
C.sub.1-C.sub.12alkyl, C.sub.3-C.sub.18alkenyl,
C.sub.5-C.sub.8cycloalkyl which is unsubstituted or substituted by
C.sub.1-C.sub.4alkyl; or benzyl unsubstituted or substituted on the
phenyl radical by C.sub.1-C.sub.4alkyl; with the proviso that the
formula (II-b) is different from ethoxycarbonyl; when n is 2, X is
C.sub.2-C.sub.6alkylene, C.sub.2-C.sub.16alkylene interrupted by
oxygen or >N--R.sub.0' with R.sub.0" being as defined below;
C.sub.2-C.sub.6alkenylene, cyclohexylene,
cyclohexylene-(C.sub.1-C.sub.4a- lkylene)-cyclohexylene,
C.sub.1-C.sub.4alkylene-cyclohexylene-C.sub.1-C.su- b.4alkylene or
C.sub.1-C.sub.4alkylene-phenylene-C.sub.1-C.sub.4alkylene, or X is
one of the groups of the formulae (III-a) to (III-j); Y.sub.1',
Y.sub.1", Y.sub.2', Y.sub.2", Y.sub.5', Y.sub.5", Y.sub.6',
Y.sub.6", Y.sub.7' and Y.sub.7" are independently of one another a
direct bond, C.sub.1-C.sub.6alkylene, cyclohexylene or phenylene;
Y.sub.3', Y.sub.3", Y.sub.4', Y.sub.4", Y.sub.8', Y.sub.8",
Y.sub.1140 , Y.sub.11", Y.sub.12' and Y.sub.12" are independently
of one another C.sub.2-C.sub.6alkylene, cyclohexylene or phenylene;
A.sub.1, A.sub.2, A.sub.3, A.sub.4, A.sub.5, A.sub.6, A.sub.7,
A.sub.8 and A.sub.9 are C.sub.2-C.sub.6alkylene,
C.sub.2-C.sub.6alkylene interrupted by oxygen or >N--R.sub.0'
with R.sub.0' being as defined below, C.sub.2-C.sub.6alkenylene,
cyclohexylene,
cyclohexylene-(C.sub.1-C.sub.4alkylene)-cyclohexylene,
C.sub.1-C.sub.4alkylene-cyclohexylene-C.sub.1-C.sub.4alkylene or
C.sub.1-C.sub.4alkylene-phenylene-C.sub.1-C.sub.4alkylene; and
A.sub.1 and A.sub.5 are additionally a direct bond; Z.sub.1',
Z.sub.2' and Z.sub.3' are independently of one another --O-- or
>N--R.sub.16'; and R.sub.0', R.sub.14' and R.sub.16' are
independently of one another hydrogen, C.sub.1-C.sub.12alkyl,
C.sub.3-C.sub.18alkenyl, C.sub.5-C.sub.8cycloalkyl which is
unsubstituted or substituted by C.sub.1-C.sub.4alkyl; or benzyl
which is unsubstituted or substituted on the phenyl radical by
C.sub.1-C.sub.4alkyl; when n is 3, X is C.sub.5-C.sub.10alkantriyl,
an aliphatic C.sub.4-C.sub.18triacyl, an aliphatic
O.sub.6--C.sub.18triacyl substituted by nitrogen; a cycloaliphatic
C.sub.6-C.sub.18triacyl, an aromatic C.sub.9-C.sub.18triacyl, a
heterocyclic C.sub.9-C.sub.18triacyl or a group of the formula
(IV); Y.sub.13', Y.sub.13" and Y.sub.13'" are independently of one
another C.sub.2-C.sub.6alkylene, cyclohexylene or phenylene;
Z.sub.1", Z.sub.2" and Z.sub.3" are independently of one another
--O-- or >N--R.sub.16"; and R.sub.16" is hydrogen,
C.sub.1-C.sub.12alkyl, C.sub.3-C.sub.18alkenyl,
C.sub.5-C.sub.8cycloalkyl which is unsubstituted or substituted by
C.sub.1-C.sub.4alkyl; or benzyl which is unsubstituted or
substituted on the phenyl radical by C.sub.1-C.sub.4alkyl; and when
n is 4, X is C.sub.15-C.sub.18alkantetrayl- , an aliphatic
C.sub.6-C.sub.18tetraacyl, an aliphatic C.sub.10-C.sub.18tetraacyl
substituted by nitrogen, a cycloaliphatic
C.sub.10-C.sub.22tetraacyl, an aromatic C.sub.10-C.sub.18tetraacyl
or a group of the formula (V); Y.sub.14' and Y.sub.14" are
independently of one another C.sub.2-C.sub.6alkylene, cyclohexylene
or phenylene; Z.sub.1'", Z.sub.2'", M and T are independently of
one another --O-- or >N--R.sub.16'", and M and T are
additionally --S--; R.sub.16'" is hydrogen, C.sub.1-C.sub.12alkyl,
C.sub.3-C.sub.18alkenyl, C.sub.5-C.sub.8cycloalkyl which is
unsubstituted or substituted by C.sub.1-C.sub.4alkyl; or benzyl
which is unsubstituted or substituted on the phenyl radical by
C.sub.1-C.sub.4alkyl; and q is an integer from 2 to 12.
11. A compound according to claim 2 wherein when n is 1, X is
C.sub.2-C.sub.6alkyl, C.sub.2-C.sub.6hydroxyalkyl,
C.sub.2-C.sub.6alkyl interrupted by oxygen; allyl, cyclohexyl,
benzyl or one of the groups of the formulae (II-a) to (II-l);
Y.sub.1, Y.sub.2, Y.sub.5, Y.sub.6, Y.sub.7 and Y.sub.9 are a
direct bond, C.sub.1-C.sub.6alkylene, cyclohexylene or phenylene;
Y.sub.3, Y.sub.4, Y.sub.8, Y.sub.10, Y.sub.11, and Y.sub.12 are
C.sub.2-C.sub.6alkylene, cyclohexylene or phenylene; R.sub.1,
R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7 and R.sub.13
are hydrogen, C.sub.1-C.sub.8alkyl, C.sub.2-C.sub.6alkyl
interrupted by oxygen; allyl, cyclohexyl, phenyl or benzyl;
Z.sub.1, Z.sub.2 and Z.sub.3 are independently of one another --O--
or >N--R.sub.16; R.sub.0, R.sub.8, R.sub.9, R.sub.10, R.sub.11,
R.sub.12, R.sub.14, R.sub.15 and R.sub.16 are independently of one
another hydrogen, C.sub.1-C.sub.6alkyl, allyl, cyclohexyl or
benzyl; with the proviso that the formula (II-b) is different from
ethoxycarbonyl; when n is 2, X is C.sub.2-C.sub.6alkylene,
C.sub.2-C.sub.14alkylene interrupted by oxygen or >N--R.sub.0';
cyclohexylene or one of the groups of the formulae (III-a) to
(III-j); Y.sub.1', Y.sub.1", Y.sub.2', Y.sub.2", Y.sub.5',
Y.sub.5", Y.sub.6', Y.sub.6", Y.sub.7' and Y.sub.7" are
independently of one another a direct bond,
C.sub.1-C.sub.6alkylene, cyclohexylene or phenylene; Y.sub.3',
Y.sub.3", Y.sub.4', Y.sub.4", Y.sub.8', Y.sub.8", Y.sub.11',
Y.sub.11", Y.sub.12' and Y.sub.12" are independently of one another
C.sub.2-C.sub.6alkylene, cyclohexylene or phenylene; A.sub.1,
A.sub.2, A.sub.3, A.sub.4, A.sub.5, A.sub.6, A.sub.7, A.sub.8 and
A.sub.9 are C.sub.2-C.sub.6alkylene, C.sub.2-C.sub.6alkylene
interrupted by oxygen; cyclohexylene or phenylene; and A.sub.1 and
A.sub.5 are additionally a direct bond; Z.sub.1', Z.sub.2' and
Z.sub.3' are independently of one another --O-- or
>N--R.sub.16'; and R.sub.0', R.sub.14' and R.sub.16' are
independently of one another hydrogen, C.sub.1-C.sub.6alkyl, allyl,
cyclohexyl or benzyl: when n is 3, X is a group of the formula
(IV); Y.sub.13', Y.sub.13" and Y.sub.13'" are independently of one
another C.sub.2-C.sub.6alkylene, cyclohexylene or phenylene;
Z.sub.1", Z.sub.2" and Z.sub.3" are independently of one another
--O-- or >N--R.sub.16"; and R.sub.16" is hydrogen,
C.sub.1-C.sub.6alkyl, allyl, cyclohexyl or benzyl; and when n is 4,
X is a group of the formula (V); Y.sub.14' and Y.sub.14" are
independently of one another C.sub.2-C.sub.6alkylene, cyclohexylene
or phenylene; Z.sub.1'", Z.sub.2'", M and T are independently of
one another --O-- or >N--R.sub.16'"; R.sub.16'" is hydrogen,
C.sub.1-C.sub.6alkyl, allyl, cyclohexyl or benzyl; and q is an
integer from 2 to 12.
12. A compound according to claim 2 wherein when n is 2, X is
C.sub.2-C.sub.6alkylene or C.sub.2-C.sub.14alkylene interrupted by
oxygen or >N--R.sub.0'; or X is a group of the formula (III-a),
(III-b) or (III-j).
13. A compound of the formula (IA) according to claim 1 wherein
G.sub.1, G.sub.2, G.sub.3 and G.sub.4 are methyl; R is
C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.12hydroxyalkyl,
C.sub.2-C.sub.8alkenyl or C.sub.5-C.sub.8cycloalkyl; when n is 1, X
is a group of the formula (II-a) or (II-l); 56Y.sub.1 is a direct
bond or C.sub.1-C.sub.6alkylene; R.sub.1 is C.sub.1-C.sub.8alkyl;
Z.sub.1, Z.sub.2 and Z.sub.3 are >N--R.sub.16; R.sub.14,
R.sub.15 and R.sub.16 are independently of one another hydrogen or
C.sub.1-C.sub.6alkyl; and Y.sub.12 is C.sub.2-C.sub.6alkylene; when
n is 2, X is C.sub.2-C.sub.6alkylene, C.sub.2-C.sub.14alkylene
interrupted by 2>N--H; or a group of the formula (III-b) or
(III-j); 57Y.sub.2', Y.sub.2", Y.sub.12' and Y.sub.12" are
independently of one another C.sub.1-C.sub.6alkylene; A.sub.2 is
C.sub.2-C.sub.6alkylene; Z.sub.1', Z.sub.2' and Z.sub.3' are
independently of one another >N--R.sub.16'; and R.sub.14' and
R.sub.16' are independently of one another hydrogen or
C.sub.1-C.sub.6alkyl; when n is 3, X is a group of the formula
(IV); 58Y.sub.13', Y.sub.13" and Y.sub.13'" are independently of
one another C.sub.2-C.sub.6alkylene; Z.sub.1", Z.sub.2" and
Z.sub.3" are a group >N--H; and when n is 4, X is a group of the
formula (V); 59Y.sub.14' and Y.sub.14" are independently of one
another C.sub.2-C.sub.6alkylene; Z.sub.1'", Z.sub.2'", M and T are
a group >N--H; and q is an integer from 2 to 6.
14. A compound of the formula (IA) according to claim 1 wherein
G.sub.1, G.sub.2, G.sub.3 and G.sub.4 are methyl; R is propyl or
2-propenyl; n is 2; X is C.sub.2-C.sub.6alkylene or a group of the
formula (III-b); 60Y.sub.2' and Y.sub.2" are independently of one
another C.sub.1-C.sub.6alkylene; and A.sub.2 is
C.sub.2-C.sub.6alkylene.
15. A compound of the formula (IA) according to claim 1 wherein n
is 2, 3 or 4.
16. A compound of the formula (IA) according to claim 1, which
corresponds to the formula 61
17. A compound of the formula (IA) according to claim 1, which
corresponds to the formula 62
18. A compound of the formula (IB) according to claim 1, wherein
G.sub.1, G.sub.2, G.sub.3 and G.sub.4 are methyl; R* is hydrogen,
C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.8alkoxy,
C.sub.3-C.sub.8alkenyloxy or C.sub.5-C.sub.8cycloalkoxy; n* is 1 or
2; Z.sub.1* and Z.sub.2* are --O-- or >N--R.sub.3*; and
R.sub.1*, R.sub.2* and R.sub.3* are independently of one another
hydrogen, C.sub.1-C.sub.6alkyl, allyl, cyclohexyl or benzyl.
19. A compound of the formula (IB) according to claim 1, wherein
G.sub.1, G.sub.2, G.sub.3 and G.sub.4 are methyl; R* is hydrogen or
C.sub.1-C.sub.4alkyl; n* is 1 or 2; Z.sub.1* and Z.sub.2* are
--O--; and R.sub.1* and R.sub.2* are independently of one another
C.sub.1-C.sub.6alkyl.
20. A compound of the formula (IB) according to claim 1, which
corresponds to the formula 63
21. A composition containing an organic material susceptible to
degradation induced by light, heat or oxidation and a compound of
the formula (IA) or (IB) according to claim 1.
22. A composition according to claim 21, which additionally
contains a conventional additive.
23. A composition according to claim 21 wherein the organic
material is a synthetic polymer.
24. A composition containing a pigmented vulcanized rubber and a
compound of the formula (IA) or (IB) according to claim 1 with the
proviso being not applied to the definition of the formula
(IA).
25. A composition containing a polyolefin and a compound of the
formula (IA) or (IB) according to claim 1 with the proviso being
not applied to the definition of the formula (IA).
26. A composition according to claim 21 wherein the organic
material is a thermoplastic polyolefin (TPO) or
acrylonitrile-butadiene-styrene (ABS).
27. A composition containing a thermoplastic polyolefin (TPO) or
acrylonitrile-butadiene-styrene (ABS) and a compound of the formula
(IA) or (IB) according to claim 1 with the proviso being not
applied to the definition of the formula (IA).
28. A recording material containing a compound of the formula (IA)
or (IB) according to claim 1 with the proviso being not applied to
the definition of the formula (IA).
29. A method for stabilizing an organic material against
degradation induced by light, heat or oxidation, which comprises
incorporating into said organic material a compound of the formula
(IA) or (IB) according to claim 1 with the proviso being not
applied to the definition of the formula (IA).
Description
[0001] The present invention relates to particular imidazolidinone
derivatives, to their use as light stabilizers, heat stabilizers
and oxidation stabilizers for organic materials, particularly
synthetic polymers, and to the organic materials thus
stabilized.
[0002] Some imidazolidinone derivatives are for example disclosed
in DE-A-2,621,947, U.S. Pat. No. 3,532,703, U.S. Pat. No.
3,971,757, WO-A-98/30601 and U.S. Pat. No. 4,448,969.
[0003] The present invention relates in particular to
[0004] a compound of the formula (IA) or (IB) 2
[0005] wherein
[0006] G.sub.1, G.sub.2, G.sub.3 and G.sub.4 are independently of
one another C.sub.1-C.sub.18alkyl or C.sub.5-C.sub.12cycloalkyl or
the radicals G.sub.1 and G.sub.2 and the radicals G.sub.3 and
G.sub.4 form independently of one another, together with the carbon
atom they are attached to, C.sub.5-C.sub.12cycloalkyl;
[0007] R is C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18hydroxyalkyl,
C.sub.2-C.sub.18alkenyl, C.sub.5-C.sub.12cycloalkyl,
C.sub.7-C.sub.12phenylalkyl unsubstituted or substituted on the
phenyl radical by C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy; or C.sub.1-C.sub.18alkanoyl;
[0008] R* is hydrogen, C.sub.1-C.sub.18alkyl, oxyl, --OH,
--CH.sub.2CN, C.sub.3-C.sub.6alkenyl, C.sub.3-C.sub.8alkynyl,
C.sub.7-C.sub.12phenylalk- yl unsubstituted or substituted on the
phenyl radical by C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy; C.sub.1-C.sub.8acyl, C.sub.1-C.sub.18alkoxy,
C.sub.1-C.sub.18hydroxyalkoxy, C.sub.2-C.sub.18alkenyloxy,
C.sub.5-C.sub.12cycloalkoxy, C.sub.7-C.sub.12phenylalkoxy
unsubstituted or substituted on the phenyl radical by
C.sub.1-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy;
C.sub.1-C.sub.18alkanoyloxy, (C.sub.1-C.sub.18alkoxy)carbonyl,
glycidyl or a group --CH.sub.2CH(OH)(G) with G being hydrogen,
methyl or phenyl;
[0009] n is 1, 2, 3 or 4;
[0010] n* is 1, 2 or 3;
[0011] X is an organic radical of a valency equal to n;
[0012] when n* is 1, X* is a group of the formula (IB-1) 3
[0013] wherein
[0014] Z.sub.1* and Z.sub.2* are independently of one another --O--
or >N--R.sub.3*;
[0015] R.sub.1*, R.sub.2* and R.sub.3* are independently of one
another hydrogen, C.sub.1-C.sub.18alkyl, C.sub.3-C.sub.18alkenyl,
C.sub.5-C.sub.12cycloalkyl which is unsubstituted or substituted by
C.sub.1-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy; or
C.sub.7-C.sub.9phenylalkyl which is unsubstituted or substituted on
the phenyl radical by C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy;
[0016] when n* is 2, X* is a group of the formula (IB-2) 4
[0017] wherein Z.sub.1* and R,* are as defined above;
[0018] when n* is 3, X* is a group of the formula (IB-3); 5
[0019] when n is 2, 3 or 4, each of the radicals G.sub.1, G.sub.2,
G.sub.3, G.sub.4 and R can have the same or a different meaning in
the units of the formula 6
[0020] when n* is 2 or 3, each of the radicals G.sub.1, G.sub.2,
G.sub.3, G.sub.4 and R* can have the same or a different meaning in
the units of the formula 7
[0021] with the proviso that when n is 1, R is methyl, ethyl,
propyl, C.sub.1-C.sub.18hydroxyalkyl, C.sub.2-C.sub.18alkenyl,
C.sub.5-C.sub.12cycloalkyl or C.sub.1-C.sub.18alkanoyl.
[0022] A preferred embodiment relates to a compound of the formula
(IA) wherein when n is 1, X is C.sub.2-C.sub.18alkyl,
C.sub.2-C.sub.18hydroxya- lkyl, C.sub.2-C.sub.18alkyl interrupted
by oxygen, sulphur or >N--R.sub.0 with R.sub.0 being as defined
below; C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18alkynyl,
C.sub.5-C.sub.12cycloal- kyl unsubstituted or substituted by --OH,
C.sub.1-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy; phenyl or
C.sub.7-C.sub.9phenylalkyl unsubstituted or substituted on the
phenyl radical by --OH, C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy; or X is one of the groups of the formulae
(II-a) to (II-m) 8
[0023] Y.sub.1, Y.sub.2, Y.sub.5, Y.sub.6, Y.sub.7 and Y.sub.9 are
a direct bond, C.sub.1-C.sub.12alkylene,
C.sub.5-C.sub.12cycloalkylene or phenylene;
[0024] Y.sub.3, Y.sub.4, Y.sub.8, Y.sub.10, Y.sub.1, and Y.sub.12
are C.sub.2-C.sub.12alkylene, C.sub.5-C.sub.12cycloalkylene or
phenylene;
[0025] R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7 and R.sub.13 are hydrogen, C.sub.1-C.sub.18alkyl,
C.sub.2-C.sub.18alkyl interrupted by oxygen, sulphur or
>N--R.sub.0 with R.sub.0 being as defined below;
C.sub.2-C.sub.18alkenyl, C.sub.2-C.sub.18alkynyl,
C.sub.5-C.sub.12cycloalkyl unsubstituted or substituted by
C.sub.1-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy; phenyl
unsubstituted or substituted by C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy; or C.sub.7-C.sub.9phenylalkyl unsubstituted
or substituted on the phenyl radical by C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy;
[0026] Z.sub.1, Z.sub.2 and Z.sub.3 are independently of one
another --O-- or >N--R.sub.16;
[0027] R.sub.0, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12,
R.sub.14, R.sub.15 and R.sub.16 are independently of one another
hydrogen, C.sub.1-C.sub.18alkyl, C.sub.3-C.sub.18alkenyl,
C.sub.5-C.sub.12cycloalky- l which is unsubstituted or substituted
by C.sub.1-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy; or
C.sub.7-C.sub.9phenylalkyl which is unsubstituted or substituted on
the phenyl radical by C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy;
[0028] with the proviso that the formula (II-b) is different from
ethoxycarbonyl;
[0029] when n is 2, X is C.sub.2-C.sub.12alkylene,
C.sub.2-C.sub.16alkylen- e interrupted by oxygen, sulphur or
>N--R.sub.0' with R.sub.0' being as defined below;
C.sub.2-C.sub.12alkenylene, C.sub.2-C.sub.12alkynylene,
C.sub.5-C.sub.12cycloalkylene,
C.sub.5-C.sub.12cycloalkylene-(C.sub.1-C.s-
ub.4alkylene)-C.sub.5-C.sub.12cycloalkylene,
C.sub.1-C.sub.4alkylene-(C.su-
b.5-C.sub.12cycloalkylene)-C.sub.1-C.sub.4alkylene, phenylene,
phenylene-(C.sub.1-C.sub.4alkylene)-phenylene or
C.sub.1-C.sub.4alkylene-- phenylene-C.sub.1-C.sub.4alkylene, or X
is one of the groups of the formulae (III-a) to (III-j) 9
[0030] Y.sub.1', Y.sub.1", Y.sub.2', Y.sub.2", Y.sub.5', Y.sub.5",
Y.sub.6', Y.sub.6", Y.sub.7' and Y.sub.7" are independently of one
another a direct bond, C.sub.1-C.sub.12alkylene,
C.sub.5-C.sub.12cycloalk- ylene or phenylene;
[0031] Y.sub.3', Y.sub.3", Y.sub.4', Y.sub.4", Y.sub.8', Y.sub.8",
Y.sub.11',Y.sub.11", Y.sub.12' and Y.sub.12" are independently of
one another C.sub.2-C.sub.12alkylene, C.sub.5-C.sub.12cycloalkylene
or phenylene;
[0032] A.sub.1, A.sub.2, A.sub.3, A.sub.4, A.sub.5, A.sub.6,
A.sub.7, A.sub.8 and A.sub.9 are C.sub.2-C.sub.12alkylene,
C.sub.2-C.sub.12alkylen- e interrupted by oxygen, sulphur or
>N--R.sub.0' with R.sub.0' being as defined below,
C.sub.2-C.sub.12alkenylene, C.sub.2-C.sub.12alkynylene,
C.sub.5-C.sub.12cycloalkylene,
C.sub.5-C.sub.12cycloalkylene-(C.sub.1-C.s-
ub.4alkylene)-C.sub.5-C.sub.12cycloalkylene,
C.sub.1-C.sub.4alkylene-(C.su-
b.5-C.sub.12cycloalkylene)-C.sub.1-C.sub.4alkylene, phenylene,
phenylene-(C.sub.1-C.sub.4alkylene)-phenylene or
C.sub.1-C.sub.4alkylene-- phenylene-C.sub.1-C.sub.4alkylene; and
A.sub.1 and A.sub.5 are additionally a direct bond;
[0033] Z.sub.1', Z.sub.2' and Z.sub.3' are independently of one
another --O-- or >N--R.sub.16'; and
[0034] R.sub.0', R.sub.14' and R.sub.16' are independently of one
another hydrogen, C.sub.1-C.sub.18alkyl, C.sub.3-C.sub.18alkenyl,
C.sub.5-C.sub.12cycloalkyl which is unsubstituted or substituted by
C.sub.1-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy; or
C.sub.7-C.sub.9phenylalkyl which is unsubstituted or substituted on
the phenyl radical by C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy:
[0035] when n is 3, X is C.sub.5-C.sub.25alkantriyl,
C.sub.4-C.sub.18triacyl or a group of the formula (IV); 10
[0036] Y.sub.13', Y.sub.13" and Y.sub.13'" are independently of one
another C.sub.2-C.sub.12alkylene, C.sub.5-C.sub.12cycloalkylene or
phenylene;
[0037] Z.sub.1", Z.sub.2" and Z.sub.3" are independently of one
another --O-- or >N--R.sub.16"; and R.sub.16" is hydrogen,
C.sub.1-C.sub.18alkyl, C.sub.3-C.sub.18alkenyl,
C.sub.5-C.sub.12cycloalky- l which is unsubstituted or substituted
by C.sub.1-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy; or
C.sub.7-C.sub.9phenylalkyl which is unsubstituted or substituted on
the phenyl radical by C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy; and
[0038] when n is 4, X is C.sub.5-C.sub.20alkantetrayl,
C.sub.6-C.sub.22tetraacyl or a group of the formula (V) 11
[0039] Y.sub.14' and Y.sub.14" are independently of one another
C.sub.2-C.sub.12alkylene, C.sub.5-C.sub.12cycloalkylene or
phenylene;
[0040] Z.sub.1'", Z.sub.2'", M and T are independently of one
another --O-- or >N--R.sub.16'", and M and T are additionally
--S--;
[0041] R.sub.16'" is hydrogen, C.sub.1-C.sub.18alkyl,
C.sub.3-C.sub.18alkenyl, C.sub.5-C.sub.12cycloalkyl which is
unsubstituted or substituted by C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy; or C.sub.7-C.sub.9phenylalkyl which is
unsubstituted or substituted on the phenyl radical by
C.sub.1-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy; and q is an
integer from 2 to 12.
[0042] X as an organic radical of a valency equal to n may be for
example an aliphatic, cycloaliphatic or aromatic residue optionally
containing a heteroatom such as oxygen, sulphur or nitrogen.
[0043] Examples of alkyl containing not more than 18 carbon atoms
are methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl,
t-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl,
t-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,
hexadecyl and octadecyl. G.sub.1, G.sub.2, G.sub.3 and G.sub.4 are
preferably C.sub.1-C.sub.4alkyl, in particular methyl.
[0044] One of the preferred meanings of R is propyl.
[0045] One of the preferred meanings of R* is C.sub.1-C.sub.4alkyl,
in particular methyl.
[0046] One of the preferred meanings of R.sub.1 is
C.sub.1-C.sub.8alkyl such as methyl or 3-heptyl.
[0047] An example of hydroxyalkyl containing not more than 18
carbon atoms is 2-hydroxyethyl or hydroxybutyl.
[0048] Examples of C.sub.2-C.sub.18alkyl interrupted by oxygen or
sulphur, e.g. one or more oxygen or sulphur, are 2-methoxyethyl,
2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-butoxypropyl,
3-octyloxypropyl, 4-methoxybutyl, 2-methylthioethyl,
2-ethylthioethyl, 3-methylthiopropyl, 3-ethylthiopropyl,
3-butylthiopropyl, 3-octylthiopropyl or 4-methylthiobutyl.
[0049] Examples of C.sub.2-C.sub.18alkyl interrupted by
>N--R.sub.0, e.g. one or more >N--R.sub.0, are
--CH.sub.2CH.sub.2--N(R.sub.0)--CH.s- ub.3,
--CH.sub.2CH.sub.2--N(R.sub.0)--CH.sub.2CH.sub.3,
--CH.sub.2CH.sub.2CH.sub.2--N(R.sub.0)--CH.sub.3 or
--CH.sub.2CH.sub.2CH.sub.2--N(R.sub.0)--CH.sub.2CH.sub.3.
[0050] Examples of alkenyl containing not more than 18 carbon atoms
are allyl, 2-methylallyl, butenyl, hexenyl, undecenyl and
octadecenyl. Alkenyls in which the carbon atom in the 1-position is
saturated are of interest, and allyl is of particular interest.
Thus, one of the preferred meanings of R is allyl. The alkenyl
groups contain only one double bond.
[0051] An example of alkynyl containing not more than 18 carbon
atoms is 2-butynyl.
[0052] Examples of alkoxy containing not more than 18 carbon atoms
are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy,
pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy,
tetradecyloxy, hexadecyloxy and octadecyloxy.
C.sub.1-C.sub.12Alkoxy, in particular methoxy, propoxy, butoxy and
octyloxy, is one of the preferred meanings of R.
[0053] 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.
[0054] Examples of C.sub.1-C.sub.18alkanoyl are formyl, acetyl,
propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl and
octanoyl.
[0055] Examples of C.sub.1-C.sub.18alkanoyloxy are formyloxy,
acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy,
heptanoyloxy and octanoyloxy.
[0056] Examples of (C.sub.1-C.sub.18alkoxy)carbonyl are
methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl,
pentyloxycarbonyl, hexyloxycarbonyl, heptyloxycarbonyl and
octyloxycarbonyl.
[0057] Examples of C.sub.5-C.sub.12cycloalkyl which is
unsubstituted or substituted by --OH, C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy, e.g. 1, 2 or 3-OH, C.sub.1-C.sub.4alkyl
and/or C.sub.1-C.sub.4alkoxy, are cyclopentyl, methylcyclopentyl,
dimethylcyclopentyl, cyclohexyl, methylcyclohexyl,
dimethylcyclohexyl, trimethylcyclohexyl, t-butylcyclohexyl,
cyclooctyl, cyclodecyl, cyclododecyl and methoxycyclohexyl.
Unsubstituted or substituted C.sub.5-C.sub.8cycloalkyl- , in
particular cyclohexyl, is preferred.
[0058] Examples of C.sub.5-C.sub.12cycloalkoxy are cyclopentoxy,
cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy,
cyclododecyloxy and methylcyclohexoxy. C.sub.5-C.sub.8Cycloalkoxy,
in particular cyclopentoxy and cyclohexoxy, is preferred.
[0059] Examples of phenyl substituted by C.sub.1-C.sub.4alkyl
and/or C.sub.1-C.sub.4alkoxy, e.g. 1, 2 or 3 C.sub.1-C.sub.4alkyl
and/or C.sub.1-C.sub.4alkoxy, are methylphenyl, dimethylphenyl,
trimethylphenyl, t-butylphenyl, di-t-butylphenyl,
3,5-di-t-butyl-4-methylphenyl, methoxyphenyl, ethoxyphenyl and
butoxyphenyl.
[0060] Examples of C.sub.7-C.sub.12phenylalkyl which is
unsubstituted or substituted on the phenyl radical by --OH,
C.sub.1-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy, e.g. 1, 2 or 3
--OH, C.sub.1-C.sub.4alkyl and/or C.sub.1-C.sub.4alkoxy, are
benzyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl,
t-butylbenzyl, 2-phenylethyl and methoxybenzyl.
C.sub.7-C.sub.9phenylalkyl, in particular benzyl, is preferred.
[0061] Examples of C.sub.7-C.sub.12phenylalkoxy unsubstituted or
substituted on the phenyl radical by C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy, e.g. 1, 2 or 3 C.sub.1-C.sub.4alkyl and/or
C.sub.1-C.sub.4alkoxy, are benzyloxy, methylbenzyloxy,
dimethylbenzyloxy, trimethylbenzyloxy, t-butylbenzyloxy,
2-phenylethoxy and methoxybenzyloxy.
[0062] C.sub.7-C.sub.9phenylalkoxy, in particular benzyloxy, is
preferred.
[0063] An example of C.sub.1-C.sub.18hydroxyalkoxy is
hydroxybutoxy.
[0064] An example of C.sub.2-C.sub.18alkenyloxy is
2-propenyloxy.
[0065] Examples of alkylene containing not more than 12 carbon
atoms are methylene, ethylene, propylene, trimethylene,
tetramethylene, pentamethylene, hexamethylene, octamethylene,
decamethylene and dodecamethylene. One of the preferred meanings of
X is C.sub.2-C.sub.12alkylene or C.sub.4-C.sub.12alkylene, in
particular C.sub.2-C.sub.6alkylene or C.sub.4-C.sub.6alkylene.
[0066] Examples of alkylene containing not more than 16 carbon
atoms and interrupted by --O-- or --S--, e.g. one or more --O-- or
--S--, are 3-oxapentane-1,5-diyl, 4-oxaheptane-1,7-diyl,
3,6-dioxaoctane-1,8-diyl, 4,7-dioxadecane-1,10-diyl,
4,9-dioxadodecane-1,12-diyl, 3,6,9-trioxaundecane-1,11-diyl,
4,7,10-trioxatridecane-1,13-diyl, 3-thiapentane-1,5-diyl,
4-thiaheptane-1,7-diyl, 3,6-dithiaoctane-1,8-diyl- ,
4,7-dithiadecane-1,10-diyl, 4,9-dithiadodecane-1,12-diyl,
3,6,9-trithiaundecane-1,11-diyl and
4,7,10-trithiatridecane-1,13-diyl.
[0067] Examples of alkylene containing not more than 16 carbon
atoms and interrupted by >N--R.sub.0', e.g. one or more
>N--R.sub.0', are
--CH.sub.2CH.sub.2--N(R.sub.0)--CH.sub.2CH.sub.2--,
--CH.sub.2CH.sub.2CH.sub.2--N(R.sub.0)--CH.sub.2CH.sub.2CH.sub.2--
and
--CH.sub.2CH.sub.2--CH(CH.sub.3)--N(R.sub.0)--CH.sub.2CH.sub.2CH.sub.2CH.-
sub.2CH.sub.2CH.sub.2--N(R.sub.0)--CH(CH.sub.3)--CH.sub.2CH.sub.2--.
[0068] One of the preferred meanings of X is
--CH.sub.2CH.sub.2--CH(CH.sub-
.3)--N(R.sub.0)--(CH.sub.2).sub.2-6--N(R.sub.0)--CH(CH.sub.3)--CH.sub.2CH.-
sub.2--.
[0069] An example of C.sub.2-C.sub.12alkenylene is
--CH.sub.2CH.dbd.CHCH.s- ub.2--. C.sub.4-C.sub.12alkenylene is
preferred.
[0070] An example of C.sub.2-C.sub.12alkynylene is
--CH.sub.2CH.sub.2--C.i- dent.C--CH.sub.2CH.sub.2--.
C.sub.6-C.sub.12alkynylene is preferred.
[0071] An example of C.sub.5-C.sub.12cycloalkylene is
cyclohexylene.
[0072] An example of
C.sub.1-C.sub.4alkylene-(C.sub.5-C.sub.12cycloalkylen-
e)-C.sub.1-C.sub.4alkylene is cyclohexylenedimethylene.
[0073] Examples of
C.sub.5-C.sub.12cycloalkylene-(C.sub.1-C.sub.4alkylene)-
-C.sub.5-C.sub.12cycloalkylene are methylenedicyclohexylene and
isopropylidenedicyclohexylene.
[0074] An example of phenylene-(C.sub.1-C.sub.4alkylene)-phenylene
is methylenediphenylene.
[0075] An example of
C.sub.1-C.sub.4alkylene-phenylene-C.sub.1-C.sub.4alky- lene is
phenylenedimethylene.
[0076] C.sub.5-C.sub.25alkantriyl may be for example a group
H.sub.3C--C(CH.sub.2).sub.3--.
[0077] C.sub.4-C.sub.18triacyl may be for example an aliphatic
C.sub.4-C.sub.18triacyl, an aliphatic C.sub.6-C.sub.18triacyl
substituted by nitrogen, a cycloaliphatic C.sub.6-C.sub.18triacyl,
an aromatic C.sub.9-C.sub.18triacyl or a heterocyclic
C.sub.9-C.sub.18triacyl.
[0078] An aliphatic C.sub.4-C.sub.18triacyl is e.g.
C.sub.4-C.sub.18alkanetrioyl unsubstituted or substituted by OH.
Preferred examples are those triacyls derived from
methanetricarboxylic acid, 1,1,2-ethanetricarboxylic acid,
1,2,3-propanetricarboxylic acid, citric acid or
1,2,3-butanetricarboxylic acid.
[0079] An aliphatic C.sub.6-C.sub.18triacyl substituted by nitrogen
is e.g. 12
[0080] The group N(CH.sub.2CO--).sub.3 is especially preferred.
[0081] A cycloaliphatic C.sub.6-C.sub.18triacyl is e.g. 13
[0082] An aromatic C.sub.9-C.sub.18triacyl is e.g. a triacyl
derived from 1,2,4-benzenetricarboxylic acid or
1,3,5-benzenetricarboxylic acid.
[0083] A heterocyclic C.sub.9-C.sub.18triacyl is e.g. a group of
the formula 14
[0084] C.sub.5-C.sub.20alkantetrayl may be for example
C(CH.sub.2).sub.4--.
[0085] A C.sub.6-C.sub.22tetraacyl is for example an aliphatic
C.sub.6-C.sub.18tetraacyl, an aliphatic C.sub.10-C.sub.18tetraacyl
substituted by nitrogen, a cycloaliphatic
C.sub.10-C.sub.22tetraacyl or an aromatic
C.sub.10-C.sub.18tetraacyl.
[0086] An aliphatic C.sub.6-C.sub.18tetraacyl is e.g.
C.sub.6-C.sub.18alkanetetraoyl. Preferred examples are those
tetraacyls derived from 1,1,3,3-propanetetracarboxylic acid or
1,2,3,4-butanetetracarboxylic acid.
[0087] An aliphatic C.sub.10-C.sub.18tetraacyl substituted by
nitrogen is e.g. a group of the formula 15
[0088] A tetraacyl derived from ethylenediaminetetraacetic acid is
preferred.
[0089] A cycloaliphatic C.sub.10-C.sub.22tetraacyl is e.g. a
cycloalkanetetracarbonyl or a cycloalkenetetracarbonyl such as
16
[0090] An aromatic C.sub.10-C.sub.18tetraacyl is for example a
tetraacyl derived from 1,2,4,5-benzenetetracarboxylic acid.
[0091] R is preferably C.sub.1-C.sub.12alkyl,
C.sub.1-C.sub.12hydroxyalkyl- , C.sub.2-C.sub.8alkenyl or
C.sub.5-C.sub.8cycloalkyl; or for example propyl,
C.sub.1-C.sub.12hydroxyalkyl, C.sub.2-C.sub.8alkenyl or
C.sub.5-C.sub.8cycloalkyl; in particular methyl, propyl, butyl,
octyl, hydroxybutyl, 2-propenyl or cyclohexyl.
[0092] R* is preferably hydrogen, C.sub.1-C.sub.4alkyl, oxyl, --OH,
C.sub.3-C.sub.6alkenyl, benzyl, C.sub.1-C.sub.8acyl,
C.sub.1-C.sub.12alkoxy, C.sub.1-C.sub.12hydroxyalkoxy,
C.sub.2-C.sub.8alkenyloxy or C.sub.5-C.sub.8cycloalkoxy, in
particular hydrogen, methyl, allyl, acetyl, methoxy, propoxy,
butoxy, octyloxy, hydroxybutoxy, 2-propenyloxy or
cyclohexyloxy.
[0093] n is preferably 2, 3 or 4, in particular 2.
[0094] A preferred embodiment of the present invention relates to a
compound of the formula (IA) wherein,
[0095] when n is 1, X is C.sub.2-C.sub.12alkyl,
C.sub.2-C.sub.12hydroxyalk- yl, C.sub.2-C.sub.12alkyl interrupted
by oxygen or >N--R.sub.0 with R.sub.0 being as defined below;
C.sub.2-C.sub.18alkenyl, C.sub.5-C.sub.8cycloalkyl unsubstituted or
substituted by C.sub.1-C.sub.4alkyl; or benzyl unsubstituted or
substituted on the phenyl radical by --OH and/or
C.sub.1-C.sub.4alkyl; or X is one of the groups of the formulae
(II-a) to (II-m);
[0096] Y.sub.1, Y.sub.2, Y.sub.5, Y.sub.6, Y.sub.7 and Y.sub.9 are
a direct bond, C.sub.1-C.sub.6alkylene, cyclohexylene or
phenylene;
[0097] Y.sub.3, Y.sub.4, Y.sub.8, Y.sub.10, Y.sub.11 and Y.sub.12
are C.sub.2-C.sub.6alkylene, cyclohexylene or phenylene;
[0098] R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7 and R.sub.13 are hydrogen, C.sub.1-C.sub.12alkyl,
C.sub.2-C.sub.12alkyl interrupted by oxygen or >N--R.sub.0 with
R.sub.0 being as defined below; C.sub.2-C.sub.18alkenyl,
C.sub.5-C.sub.8cycloalkyl unsubstituted or substituted by
C.sub.1-C.sub.4alkyl; phenyl unsubstituted or substituted by
C.sub.1-C.sub.4alkyl; or benzyl unsubstituted or substituted on the
phenyl radical by C.sub.1-C.sub.4alkyl;
[0099] Z.sub.1, Z.sub.2 and Z.sub.3 are independently of one
another --O-- or >N--R.sub.16;
[0100] R.sub.0, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12,
R.sub.14, R.sub.15 and R.sub.16 are independently of one another
hydrogen, C.sub.1-C.sub.12alkyl, C.sub.3-C.sub.18alkenyl,
C.sub.5-C.sub.8cycloalkyl which is unsubstituted or substituted by
C.sub.1-C.sub.4alkyl; or benzyl unsubstituted or substituted on the
phenyl radical by C.sub.1-C.sub.4alkyl; with the proviso that the
formula (II-b) is different from ethoxycarbonyl;
[0101] when n is 2, X is C.sub.2-C.sub.6alkylene,
C.sub.2-C.sub.16alkylene interrupted by oxygen or >N--R.sub.0'
with R.sub.0' being as defined below; C.sub.2-C.sub.6alkenylene,
cyclohexylene, cyclohexylene-(C.sub.1-C-
.sub.4alkylene)-cyclohexylene,
C.sub.1-C.sub.4alkylene-cyclohexylene-C.sub- .1-C.sub.4alkylene or
C.sub.1-C.sub.4alkylene-phenylene-C.sub.1-C.sub.4alk- ylene, or X
is one of the groups of the formulae (III-a) to (III-j);
[0102] Y.sub.1', Y.sub.1", Y.sub.2', Y.sub.2", Y.sub.5', Y.sub.5",
Y.sub.6', Y.sub.6", Y.sub.7' and Y.sub.7" are independently of one
another a direct bond, C.sub.1-C.sub.6alkylene, cyclohexylene or
phenylene;
[0103] Y.sub.3', Y.sub.3", Y.sub.4', Y.sub.4", Y.sub.8', Y.sub.8",
Y.sub.11', Y.sub.11", Y.sub.12' and Y.sub.12" are independently of
one another C.sub.2-C.sub.6alkylene, cyclohexylene or
phenylene;
[0104] A.sub.1, A.sub.2, A.sub.3, A.sub.4, A.sub.5, A.sub.6,
A.sub.7, A.sub.8 and A.sub.9 are C.sub.2-C.sub.6alkylene,
C.sub.2-C.sub.6alkylene interrupted by oxygen or >N--R.sub.0'
with R.sub.0' being as defined below, C.sub.2-C.sub.6alkenylene,
cyclohexylene, cyclohexylene-(C.sub.1-C-
.sub.4alkylene)-cyclohexylene,
C.sub.1-C.sub.4alkylene-cyclohexylene-C.sub- .1-C.sub.4alkylene or
C.sub.1-C.sub.4alkylene-phenylene-C.sub.1-C.sub.4alk- ylene; and
A.sub.1 and A.sub.5 are additionally a direct bond;
[0105] Z.sub.1', Z.sub.2' and Z.sub.3' are independently of one
another --O-- or >N--R.sub.6'; and
[0106] R.sub.0', R.sub.14' and R.sub.16' are independently of one
another hydrogen, C.sub.1-C.sub.12alkyl, C.sub.3-C.sub.18alkenyl,
C.sub.5-C.sub.8cycloalkyl which is unsubstituted or substituted by
C.sub.1-C.sub.4alkyl; or benzyl which is unsubstituted or
substituted on the phenyl radical by C.sub.1-C.sub.4alkyl;
[0107] when n is 3, X is C.sub.5-C.sub.10alkantriyl, an aliphatic
C.sub.4-C.sub.18triacyl, an aliphatic C.sub.6-C.sub.18triacyl
substituted by nitrogen; a cycloaliphatic C.sub.6-C.sub.18triacyl,
an aromatic C.sub.9-C.sub.18triacyl, a heterocyclic
C.sub.9-C.sub.18triacyl or a group of the formula (IV);
[0108] Y.sub.13', Y.sub.13" and Y.sub.13'" are independently of one
another C.sub.2-C.sub.6alkylene, cyclohexylene or phenylene;
[0109] Z.sub.1", Z.sub.2" and Z.sub.3" are independently of one
another --O-- or >N--R.sub.16"; and
[0110] R.sub.16" is hydrogen, C.sub.1-C.sub.12alkyl,
C.sub.3-C.sub.18alkenyl, C.sub.5-C.sub.8cycloalkyl which is
unsubstituted or substituted by C.sub.1-C.sub.4alkyl; or benzyl
which is unsubstituted or substituted on the phenyl radical by
C.sub.1-C.sub.4alkyl; and
[0111] when n is 4, X is C.sub.5-C.sub.10alkantetrayl, an aliphatic
C.sub.6-C.sub.18tetraacyl, an aliphatic C.sub.10-C.sub.18tetraacyl
substituted by nitrogen, a cycloaliphatic
C.sub.10-C.sub.22tetraacyl, an aromatic C.sub.10-C.sub.18tetraacyl
or a group of the formula (V);
[0112] Y.sub.14' and Y.sub.14" are independently of one another
C.sub.2-C.sub.6alkylene, cyclohexylene or phenylene;
[0113] Z.sub.1'", Z.sub.2'", M and T are independently of one
another --O-- or >N--R.sub.16'", and M and T are additionally
--S--;
[0114] R.sub.16'" is hydrogen, C.sub.1-C.sub.12alkyl,
C.sub.3-C.sub.18alkenyl, C.sub.5-C.sub.8cycloalkyl which is
unsubstituted or substituted by C.sub.1-C.sub.4alkyl; or benzyl
which is unsubstituted or substituted on the phenyl radical by
C.sub.1-C.sub.4alkyl; and
[0115] q is an integer from 2 to 12.
[0116] A further preferred embodiment of the present invention
relates to a compound of the formula (IA) wherein,
[0117] when n is 1, X is C.sub.2-C.sub.6alkyl,
C.sub.2-C.sub.6hydroxyalkyl- , C.sub.2-C.sub.6alkyl interrupted by
oxygen; allyl, cyclohexyl, benzyl or one of the groups of the
formulae (II-a) to (II-l);
[0118] Y.sub.1, Y.sub.2, Y.sub.5, Y.sub.6, Y.sub.7 and Y.sub.9 are
a direct bond, C.sub.1-C.sub.6alkylene, cyclohexylene or
phenylene;
[0119] Y.sub.3, Y.sub.4, Y.sub.8, Y.sub.10, Y.sub.1, and Y.sub.12
are C.sub.2-C.sub.6alkylene, cyclohexylene or phenylene;
[0120] R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6,
R.sub.7 and R.sub.13 are hydrogen, C.sub.1-C.sub.8alkyl,
C.sub.2-C.sub.6alkyl interrupted by oxygen;
[0121] allyl, cyclohexyl, phenyl or benzyl;
[0122] Z.sub.1, Z.sub.2 and Z.sub.3 are independently of one
another --O-- or >N--R.sub.16;
[0123] R.sub.0, R.sub.8, R.sub.9, R.sub.10, R.sub.11, R.sub.12,
R.sub.14, R.sub.15 and R.sub.16 are independently of one another
hydrogen, C.sub.1-C.sub.6alkyl, allyl, cyclohexyl or benzyl;
[0124] with the proviso that the formula (II-b) is different from
ethoxycarbonyl;
[0125] when n is 2, X is C.sub.2-C.sub.6alkylene,
C.sub.2-C.sub.14alkylene interrupted by oxygen or
>N--R.sub.0';
[0126] cyclohexylene or one of the groups of the formulae (III-a)
to (III-j);
[0127] Y.sub.1', Y.sub.1", Y.sub.2', Y.sub.2", Y.sub.5', Y.sub.5",
Y.sub.6', Y.sub.6", Y.sub.7' and Y.sub.7" are independently of one
another a direct bond, C.sub.1-C.sub.6alkylene, cyclohexylene or
phenylene;
[0128] Y.sub.3', Y.sub.3", Y.sub.4', Y.sub.4", Y.sub.8', Y.sub.8",
Y.sub.11', Y.sub.11", Y.sub.12' and Y.sub.12" are independently of
one another C.sub.2-C.sub.6alkylene, cyclohexylene or
phenylene;
[0129] A.sub.1, A.sub.2, A.sub.3, A.sub.4, A.sub.5, A.sub.6,
A.sub.7, A.sub.8 and A.sub.9 are C.sub.2-C.sub.6alkylene,
C.sub.2-C.sub.6alkylene interrupted by oxygen;
[0130] cyclohexylene or phenylene; and A.sub.1 and A.sub.5 are
additionally a direct bond;
[0131] Z.sub.1', Z.sub.2' and Z.sub.3' are independently of one
another --O-- or >N--R.sub.16'; and
[0132] R.sub.0', R.sub.14' and R.sub.16' are independently of one
another hydrogen, C.sub.1-C.sub.6alkyl, allyl, cyclohexyl or
benzyl:
[0133] when n is 3, X is a group of the formula (IV);
[0134] Y.sub.13', Y.sub.13" and Y.sub.13'" are independently of one
another C.sub.2-C.sub.6alkylene, cyclohexylene or phenylene;
[0135] Z.sub.1", Z.sub.2" and Z.sub.3" are independently of one
another --O-- or >N--R.sub.16"; and
[0136] R.sub.16" is hydrogen, C.sub.1-C.sub.6alkyl, allyl,
cyclohexyl or benzyl; and
[0137] when n is 4, X is a group of the formula (V);
[0138] Y.sub.14' and Y.sub.14" are independently of one another
C.sub.2-C.sub.6alkylene, cyclohexylene or phenylene;
[0139] Z.sub.1'", Z.sub.2'", M and T are independently of one
another --O-- or >N--R.sub.16'";
[0140] R.sub.16'" is hydrogen, C.sub.1-C.sub.6alkyl, allyl,
cyclohexyl or benzyl; and q is an integer from 2 to 12.
[0141] When n is 2, X is preferably C.sub.2-C.sub.6alkylene or
C.sub.2-C.sub.14alkylene interrupted by oxygen or >N--R.sub.0';
or X is a group of the formula (III-a), (III-b) or (III-j).
[0142] Also preferred is a compound of the formula (IA) wherein
[0143] G.sub.1, G.sub.2, G.sub.3 and G.sub.4 are methyl;
[0144] R is C.sub.1-C.sub.12alkyl, C.sub.1-C.sub.12hydroxyalkyl,
C.sub.2-C.sub.8alkenyl or C.sub.5-C.sub.8cycloalkyl;
[0145] when n is 1, X is a group of the formula (II-a) or (II-l);
17
[0146] Y.sub.1 is a direct bond or C.sub.1-C.sub.6alkylene;
[0147] R.sub.1 is C.sub.1-C.sub.8alkyl;
[0148] Z.sub.1, Z.sub.2 and Z.sub.3 are >N--R.sub.16;
[0149] R.sub.14, R.sub.15 and R.sub.16 are independently of one
another hydrogen or C.sub.1-C.sub.6alkyl; and
[0150] Y.sub.12 is C.sub.2-C.sub.6alkylene;
[0151] when n is 2, X is C.sub.2-C.sub.6alkylene,
C.sub.2-C.sub.14alkylene interrupted by 2>N--H; or a group of
the formula (III-b) or (III-j); 18
[0152] Y.sub.2', Y.sub.2", Y.sub.12' and Y.sub.12" are
independently of one another C.sub.1-C.sub.6alkylene;
[0153] A.sub.2 is C.sub.2-C.sub.6alkylene;
[0154] Z.sub.1', Z.sub.2' and Z.sub.3' are independently of one
another >N--R.sub.16'; and
[0155] R.sub.14' and R.sub.16' are independently of one another
hydrogen or C.sub.1-C.sub.6alkyl;
[0156] when n is 3, X is-a group of the formula (IV); 19
[0157] Y.sub.13', Y.sub.13" and Y.sub.13'" are independently of one
another C.sub.2-C.sub.6alkylene;
[0158] Z.sub.1", Z.sub.2" and Z.sub.3" are a group >N--H;
and
[0159] when n is 4, X is a group of the formula (V); 20
[0160] Y.sub.14' and Y.sub.14" are independently of one another
C.sub.2-C.sub.6alkylene;
[0161] Z.sub.1'", Z.sub.2'", M and T are a group >N--H; and
[0162] q is an integer from 2 to 6.
[0163] A compound of the formula (IA) which is of interest is one
wherein
[0164] G.sub.1, G.sub.2, G.sub.3 and G.sub.4 are methyl;
[0165] R is propyl or 2-propenyl;
[0166] n is 2;
[0167] X is C.sub.2-C.sub.6alkylene or a group of the formula
(III-b); 21
[0168] Y.sub.2' and Y.sub.2" are independently of one another
C.sub.1-C.sub.6alkylene; and
[0169] A.sub.2 is C.sub.2-C.sub.6alkylene.
[0170] Examples of compounds of the formula (IA) are: 22
[0171] Particularly preferred examples of the compounds of the
formula (IA) are: 23
[0172] Another preferred embodiment of the present invention
relates to a compound of the formula (IB) wherein
[0173] G.sub.1, G.sub.2, G.sub.3 and G.sub.4 are methyl;
[0174] R* is hydrogen, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.8alkoxy,
C.sub.3-C.sub.8alkenyloxy or C.sub.5-C.sub.8cycloalkoxy;
[0175] n* is 1 or 2;
[0176] Z.sub.1* and Z.sub.2* are --O-- or >N--R.sub.3*; and
[0177] R.sub.1*, R.sub.2* and R.sub.3* are independently of one
another hydrogen, C.sub.1-C.sub.6alkyl, allyl, cyclohexyl or
benzyl.
[0178] A further preferred embodiment of the present invention
relates to a compound of the formula (IB) wherein
[0179] G.sub.1, G.sub.2, G.sub.3 and G.sub.4 are methyl;
[0180] R* is hydrogen or C.sub.1-C.sub.4alkyl;
[0181] n* is 1 or 2;
[0182] Z.sub.1* and Z.sub.2* are --O--; and
[0183] R.sub.1* and R.sub.2* are independently of one another
C.sub.1-C.sub.6alkyl.
[0184] Examples of compounds of the formula (IB) are 24
[0185] The compounds of the formulae (IA) and (IB) can be prepared,
for example, according to the following reaction scheme. 25
[0186] wherein G.sub.1, G.sub.2, G.sub.3, G.sub.4, X and X* as well
as n and n* are as defined above and Hal means e.g. Br, Cl or J,
preferably Cl or Br.
[0187] The reaction can be carried out without the isolation of the
ionic intermediate. Suitable organic solvents are common aprotic
organic solvents, for example toluene, xylene, mesitylene or
tetrahydrofuran, in particular toluene. The ratio of the reactants
is preferably stoichiometric but it is also possible to use the
imidazolidinone in an excess of up to 40 mol %. Examples of
suitable bases are potassium tert-butoxide, potassium hydroxide and
sodium hydroxide. A preferred base is potassium tert-butoxide. The
base can be applied in an excess of up to 20 mol %. The reaction
temperature is for example from room temperature to 80.degree. C.,
preferably 30-40.degree. C.
[0188] The substitution of the nitrogen >N--H of the final
product (that means the introduction of the radical R* different
from hydrogen or the introduction of the radical --OR) can be
carried out according to known processes.
[0189] The imidazolidinone starting material is known and can be
prepared in analogy to known processes. When G.sub.1, G.sub.2,
G.sub.3 and G.sub.4 are methyl, it can also be prepared as shown in
SCHEME 2 below. 26
[0190] These reactions are described in EXAMPLE 1, steps 1.1 and
1.2.
[0191] The preparation of the compounds according to the present
invention is shown in more detail in the working examples.
[0192] The compounds of this invention are very effective in
improving the light, heat and oxidation resistance of organic
materials.
[0193] Examples of such organic materials are:
[0194] 1. Polymers of monoolefins and diolefins, for example
polypropylene, polyisobutylene, polybut-1-ene,
poly-4-methylpent-1-ene, polyvinylcyclohexane, 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).
[0195] 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:
[0196] a) radical polymerisation (normally under high pressure and
at elevated temperature).
[0197] 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).
[0198] 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).
[0199] 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, ethylene/vinylcyclohexane copolymers,
ethylene/cycloolefin copolymers (e.g. ethylene/norbornene like
COC), ethylene/1-olefins copolymers, where the 1-olefin is
gene-rated in-situ; propylene/butadiene copolymers,
isobutylene/isoprene copolymers, ethylene/vinylcyclohexene
copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl
methacrylate copolymers, ethylene/vinyl acetate copolymers or
ethylene/acrylic acid copolymers and their salts (ionomers) as well
as terpolymers of ethylene with propylene and a diene such as
hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures
of such copolymers with one another and with polymers mentioned in
1) above, for example polypropylene/ethylene-propylene copolymers,
LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic
acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or
random polyalkylene/carbon monoxide copolymers and mixtures thereof
with other polymers, for example polyamides.
[0200] 4. Hydrocarbon resins (for example C.sub.5-C.sub.9)
including hydrogenated modifications thereof (e.g. tackifiers) and
mixtures of polyalkylenes and starch.
[0201] Homopolymers and copolymers from 1.)-4.) may have any
stereostructure including syndiotactic, isotactic, hemi-isotactic
or atactic; where atactic polymers are preferred. Stereoblock
polymers are also included.
[0202] 5. Polystyrene, poly(p-methylstyrene),
poly(.alpha.-methylstyrene).
[0203] 6. Aromatic homopolymers and copolymers derived from vinyl
aromatic monomers including styrene, .alpha.-methylstyrene, all
isomers of vinyl toluene, especially p-vinyltoluene, all isomers of
ethyl styrene, propyl styrene, vinyl biphenyl, vinyl naphthalene,
and vinyl anthracene, and mixtures thereof. Homopolymers and
copolymers may have any stereostructure including syndiotactic,
isotactic, hemi-isotactic or atactic; where atactic polymers are
preferred. Stereoblock polymers are also included.
[0204] 6a. Copolymers including aforementioned vinyl aromatic
monomers and comonomers selected from ethylene, propylene, dienes,
nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and
vinyl chloride or acrylic derivatives and mixtures thereof, for
example styrene/butadiene, styrene/acrylonitrile, styrene/ethylene
(interpolymers), 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.
[0205] 6b. Hydrogenated aromatic polymers derived from
hydrogenation of polymers mentioned under 6.), especially including
polycyclohexylethylene (PCHE) prepared by hydrogenating atactic
polystyrene, often referred to as polyvinylcyclohexane (PVCH).
[0206] 6c. Hydrogenated aromatic polymers derived from
hydrogenation of polymers mentioned under 6a.).
[0207] Homopolymers and copolymers may have any stereostructure
including syndiotactic, isotactic, hemi-isotactic or atactic; where
atactic polymers are preferred. Stereoblock polymers are also
included.
[0208] 7. Graft copolymers of vinyl aromatic monomers such as
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.
[0209] 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.
[0210] 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.
[0211] 10. Copolymers of the monomers mentioned under 9) with each
other or with other unsaturated monomers, for example
acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate
copolymers, acrylonitrile/alkoxyalkyl acrylate or
acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl
methacrylate/butadiene terpolymers.
[0212] 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.
[0213] 12. Homopolymers and copolymers of cyclic ethers such as
polyalkylene glycols, polyethylene oxide, polypropylene oxide or
copolymers thereof with bisglycidyl ethers.
[0214] 13. Polyacetals such as polyoxymethylene and those
polyoxymethylenes which contain ethylene oxide as a comonomer;
polyacetals modified with thermoplastic polyurethanes, acrylates or
MBS.
[0215] 14. Polyphenylene oxides and sulfides, and mixtures of
polyphenylene oxides with styrene polymers or polyamides.
[0216] 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.
[0217] 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).
[0218] 17. Polyureas, polyimides, polyamide-imides, polyetherimids,
polyesterimids, polyhydantoins and polybenzimidazoles.
[0219] 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.
[0220] 19. Polycarbonates and polyester carbonates.
[0221] 20. Polyketones.
[0222] 21. Polysulfones, polyether sulfones and polyether
ketones.
[0223] 22. 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.
[0224] 23. Drying and non-drying alkyd resins.
[0225] 24. 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.
[0226] 25. Crosslinkable acrylic resins derived from substituted
acrylates, for example epoxy acrylates, urethane acrylates or
polyester acrylates.
[0227] 26. Alkyd resins, polyester resins and acrylate resins
crosslinked with melamine resins, urea resins, isocyanates,
isocyanurates, polyisocyanates or epoxy resins.
[0228] 27. 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.
[0229] 28. 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.
[0230] 29. 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.
[0231] 30. 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.
[0232] 31. Aqueous emulsions of natural or synthetic rubber, e.g.
natural latex or latices of carboxylated styrene/butadiene
copolymers.
[0233] Thus, the invention also relates to a composition containing
an organic material susceptible to degradation induced by light,
heat or oxidation and a compound of the formula (IA) or (IB) as
described above.
[0234] The organic material is preferably a synthetic polymer, more
particularly one selected from the aforementioned groups. The
synthetic polymer is for example a thermoplastic polyolefin (TPO),
a thermoplastic elastomer (TPE) or a thermoplastic vulcanizate
(TPV).
[0235] Polyolefins are preferred. Thermoplastic polyolefins (TPO)
or acrylonitrile-butadiene-styrene (ABS) are also preferred.
[0236] The compounds of the formula (IA) or (IB) are further useful
as corrosion inhibitors and also as light stabilizers for coatings.
Thus, a further preferred embodiment of the present invention
relates to a coating containing a compound of the formula (IA) or
(IB). Suitable coatings are for example described in U.S. Pat. No.
6,117,997, column 26, line 55 to column 32, line 21.
[0237] Pigmented vulcanized rubbers or pigmented thermoplastic
elastomers containing a compound of the formula (IA) or (IB) with
the proviso being not applied to the definition of the formula (IA)
are a particularly preferred embodiment of this invention. A
pigmented (non black) rubber vulcanizate contains for example
elastomers, vulcanizing agents, accelerators, accelerator
activators, age-resistors, fillers/pigments, softeners and some
further miscellaneous ingredients.
[0238] Examples of elastomers are polyisoprene or polybutadiene;
copolymers of monoolefins and diolefins with each other or with
other vinyl monomers, e.g. ethylene/octene copolymers,
propylene/butadiene copolymers, isobutylene/isoprene copolymers,
ethylene/alkyl acrylate copolymers or ethylene/alkyl methacrylate
copolymers; 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 above in 1); copolymers of styrene or
.alpha.-methylstyrene with dienes or acrylic derivatives, for
example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl
methacrylate, styrene/butadiene/alkyl acrylate or
styrene/butadiene/alkyl methacrylate; block copolymers of styrene
such as styrene/butadiene/styrene, styrene/isoprene/styrene,
styrene/ethylene/butylene/styrene or
styrene/ethylene/propylene/styrene; halogen-containing polymers
such as polychloroprene, chlorinated rubbers, chlorinated and
brominated copolymer of isobutylene-isoprene (halobutyl rubber) or
chlorinated or sulfochlorinated polyethylene; copolymers of the
monomers mentioned above under 9) with each other or with other
unsaturated monomers, for example acrylonitrile/butadiene
copolymers; polyblends such as PP/EPDM, poly-amide/EPDM or ABS; or
aqueous emulsions of natural or synthetic rubber, e.g. natural
latex or latices of carboxylated styrene/butadiene copolymers.
[0239] Vulcanizing agents are chemicals that are required to
crosslink the rubber chains into the three-dimensional network
which gives the desired physical properties in the final product.
The most common agent used is sulfur and sulfur-bearing chemicals
(sulfur donors). Examples of agents which are used for non-sulfur
vulcanization are metal oxides, di- or polyfunctional compounds and
peroxides.
[0240] Accelerators are generally needed for sulfur-crosslinking.
These chemicals reduce the time required for vulcanization and
improve the properties of the vulcanizate. Accelerators belong
mainly to the following chemical groups: amines (e.g. hexamethylene
tetramins), guanidines (e.g. diphenyl guanidine), thioureas,
thiazoles, thiurams, sulfenamides or dithiocarbamates.
[0241] Accelerator activators are components used to increase the
vulcanization rate by activating the accelerator so that it
performs more effectively. Accelerator activators are for example
inorganic compounds (mainly metal oxides) such as zinc oxide, red
lead, magnesium oxide or alkali carbonates. The most common
accelerator activator is zinc oxide. Further, accelerator
activators can also be organic acids (normally used in combination
with metal oxides) such as high molecular weight monobasic acids or
mixtures thereof. Examples are stearic acid, oleic acid, lauric
acid, palmitic acid and myristic acid.
[0242] Age-resisters are usually selected from the below-mentioned
list of conventional additives.
[0243] Fillers may either reinforce, extend, dilute, or impart
certain properties to rubbers. Carbon black is normally used for
black formulations. For non-black colored formulations, fillers and
pigments from the following classes of mineral fillers can be used:
Pyrogenic or precipitated silica, calcium silicate, calcium
carbonate, china clay and hard clay.
[0244] Examples of further miscellaneous ingredients are:
[0245] a) colorants or pigments such as titanium dioxide, zinc
oxide, zinc sulfide, iron oxide, Microlen (RTM) Yellow 3G, Microlen
(RTM) DPP Red BP, Microlen (RTM) Green GFN, Ciba (RTM) IRGACOLOR
(RTM) Yellow 2GLMA, Ciba (RTM) IRGACOLOR (RTM) Yellow 2GTM, Ciba
(RTM) CROMOPHTAL (RTM) Yellow 8GN, Ciba (RTM) IRGAZIN (RTM) Yellow
2GLTE, Ciba (RTM) IRGALITE (RTM) Yellow WGP, Ciba (RTM) CROMOPHTAL
(RTM) Yellow 3G, Ciba (RTM) IRGALITE (RTM) Yellow WSR, Ciba (RTM)
IRGALITE (RTM) Yellow BAWP, Ciba (RTM) CROMOPHTAL (RTM) Yellow GR,
Ciba (RTM) CROMOPHTAL (RTM) Yellow GT-AD, Ciba (RTM) CROMOPHTAL
(RTM) Yellow HRP, Ciba (RTM) CROMOPHTAL (RTM) Yellow 2RF, Ciba
(RTM) CROMOPHTAL (RTM) Yellow 2RLTS, Ciba (RTM) CROMOPHTAL (RTM)
Yellow 2RLP, Ciba (RTM) IRGAZIN (RTM) Yellow 3RLTN, Ciba (RTM)
CROMOPHTAL (RTM) Orange 2G, Ciba (RTM) CROMOPHTAL (RTM) DPP Orange
TRP, Ciba (RTM) CROMOPHTAL (RTM) Orange GP, Ciba (RTM) IRGALITE
(RTM) Orange F2G, Ciba (RTM) IRGAZIN (RTM) DPP Orange RA, Ciba
(RTM) CROMOPHTAL (RTM) Brown 5R, Ciba (RTM) CROMOPHTAL (RTM)
Scarlet RN, Ciba (RTM) IRGALITE (RTM) Red LCB, Ciba (RTM) IRGALITE
(RTM) Red 2BY, Ciba (RTM) CROMOPHTAL (RTM) DPP Flame Red EP, Ciba
(RTM) CROMOPHTAL (RTM) Red G, Ciba (RTM) CROMOPHTAL (RTM) DPP Red
BOC, Ciba (RTM) IRGAZIN (RTM) DPP Red BO, Ciba (RTM) CROMOPHTAL
(RTM) DPP Red BP, Ciba (RTM) CROMOPHTAL (RTM) Red 2030, Ciba (RTM)
IRGAZIN (RTM) DPP Red BTR, Ciba (RTM) CROMOPHTAL (RTM) Red BRN,
Ciba (RTM) CROMOPHTAL (RTM) Red BN, Ciba (RTM) IRGALITE (RTM) Red
2BSP, Ciba (RTM) IRGAZIN (RTM) DPP Rubine TR, Ciba (RTM) CROMOPHTAL
(RTM) Red A3B, Ciba (RTM) CROMOPHTAL (RTM) Red 2B, Ciba (RTM)
CROMOPHTAL (RTM) Red 2020, Ciba (RTM) CINQUASIA (RTM) Red Y
RT-759-D, Ciba (RTM) IRGALITE (RTM) Red 2BP, Ciba (RTM) CINQUASIA
(RTM) Red B RT-790-D, Ciba (RTM) IRGALITE (RTM) Rubine 4BP, Ciba
(RTM) CINQUASIA (RTM) Red B RT-195-D, Ciba (RTM) CINQUASIA (RTM)
Magenta RT-235-D, Ciba (RTM) CINQUASIA (RTM) Violet R RT-891-D,
Ciba (RTM) CROMOPHTAL (RTM) Violet B, Ciba (RTM) CROMOPHTAL (RTM)
Violet GT, Ciba (RTM) CROMOPHTAL (RTM) Blue A3R, Ciba (RTM)
IRGALITE (RTM) Blue BLPO, Ciba (RTM) IRGALITE (RTM) Blue BSP, Ciba
(RTM) CROMOPHTAL (RTM) Blue 4GNP, Ciba (RTM) IRGALITE (RTM) Blue
GBP, Ciba (RTM) IRGALITE (RTM) Green GFNP; b) blowing agents, c)
flame retardants, d) retarders, e) odorants, and f) abrasives.
[0246] In pigmented vulcanized rubbers or pigmented thermoplastic
elastomers, the compound of the formula (IA) or (IB) is preferably
applied together with an UV absorber, in particular one of those
listed in group 2 of the list of conventional additives further
below. The combination of one of the compounds of Examples 1 to 6
of this invention with .RTM.TINUVIN 213 which is the
transesterification product of
2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotr-
iazole with polyethylene glycol 300 is particularly preferred.
[0247] A further embodiment of this invention is a method for
stabilizing an organic material against degradation induced by
light, heat or oxidation, which comprises incorporating into said
organic material at least one compound of the formula (IA) or (IB)
with the proviso being not applied to the definition of the formula
(IA).
[0248] The compounds of this invention can be used in various
proportions depending on the nature of the material to be
stabilized, on the end use and on the presence of other additives.
In general, it is appropriate to use for example 0.01 to 10% or
0.01 to 5% of the compound of the formula (IA) or (IB), relative to
the weight of-the material to be stabilized (or the rubber
content), preferably 0.05 to 2% or 0.05 to 1% or 0.1 to 5% or 0.2
to 3%.
[0249] The compounds of this invention can be added, for example,
to the polymeric materials before, during or after the
polymerization or crosslinking of the said materials. Furthermore,
they can be incorporated in the polymeric materials in the pure
form or encapsulated in waxes, oils or polymers.
[0250] In general, the compounds of this invention can be
incorporated in the polymeric materials by various processes, such
as dry mixing in the form of powder, or wet mixing in the form of
solutions or suspensions or also in the form of a masterbatch which
contains the compounds of this invention in a concentration of 2.5
to 25% by weight; in such operations, the polymer can be used in
the form of powder, granules, solutions, suspensions or in the form
of latices.
[0251] The materials stabilized with the compounds of this
invention can be used for the production of mouldings, films,
tapes, monofilaments, fibres, surface coatings and the like; or
colored tires, weathering strips, gaskets, sealings, roofing
membranes, various technical rubber articles (hose, tubes) or
boots.
[0252] If desired, other conventional additives for synthetic
polymers, such as antioxidants, UV absorbers, nickel stabilizers,
pigments, fillers, plasticizers, corrosion inhibitors and metal
deactivators, can be added to the organic materials containing the
compounds of this invention.
[0253] Particular examples of said conventional additives are:
[0254] 1. Antioxidants
[0255] 1.1. Alkylated monophenols, for example
2,6-di-tert-butyl-4-methylp- henol,
2-tert-butyl-4,6-di-methylphenol, 2,6-di-tert-butyl-4-ethylphenol,
2,6-di-tert-butyl-4-n-butylphenol,
2,6-di-tert-butyl-4-isobutylphenol,
2,6-dicyclopentyl-4-methylphenol,
2-(a-methylcyclohexyl)-4,6-dimethylphen- ol,
2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol,
2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which are
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.
[0256] 1.2. Alkylthiomethylphenols, for example
2,4-dioctylthiomethyl-6-te- rt-butylphenol,
2,4-dioctylthiomethyl-6-methylphenol,
2,4-dioctylthiomethyl-6-ethylphenol,
2,6-di-dodecylthiomethyl-4-nonylphen- ol.
[0257] 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.
[0258] 1.4. Tocopherols, for example .alpha.-tocopherol,
.beta.-tocopherol, .gamma.-tocopherol, 8-tocopherol and mixtures
thereof (vitamin E).
[0259] 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.
[0260] 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-butyl-phenol),
2,2'-ethylidenebis(6-tert-b- utyl-4-isobutylphenol),
2,2'-methylenebis[6-(.alpha.-methylbenzyl)-4-nonyl- phenol],
2,2'-methylenebis[6-(.alpha.,.alpha.-dimethylbenzyl)-4-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-methylphenyl)-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-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane,
1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
[0261] 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-hydroxyben- zyl)sulfide,
isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
[0262] 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,
didodecylmercaptoethyl-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-butyl-4-hydr-
oxybenzyl)malonate.
[0263] 1.9. Aromatic hydroxybenzyl compounds, for example
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,
1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
[0264] 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-hydroxy-phenylpropionyl)-hexahydro-1,3,5-t-
riazine,
1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.
[0265] 1.11. Benzylphosphonates, for example
dimethyl-2,5-di-tert-butyl-4-- hydroxybenzylphosphonate,
diethyl-3,5-di-tert-butyl-4-hydroxybenzylphospho- nate,
dioctadecyl3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the
calcium salt of the monoethyl ester of
3,5-di-tert-butyl-4-hydroxybenzylphosphoni- c acid.
[0266] 1.12. Acylaminophenols, for example 4-hydroxylauranilide,
4-hydroxystearanilide, octyl
N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbama- te.
[0267] 1.13. Esters of
.beta.-(3,5-di-tert-butyl-4-hydroxaphenyl)prorpioni- c acid with
mono- or polyhydric alcohols, e.g. with methanol, ethanol,
n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene
glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]o- ctane.
[0268] 1.14. Esters of
.beta.-(5-tert-butyl-4-hydroxy-3-methylphenyl)propi- onic acid with
mono- or polyhydric alcohols, e.g. with methanol, ethanol,
n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene
glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis-(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]o- ctane;
3,9-bis[2-{3-(3-tertbutyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,-
1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]-undecane.
[0269] 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)isocyanura- te, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7--
trioxabicyclo[2.2.2]octane.
[0270] 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic
acid with mono- or polyhydric alcohols, e.g. with methanol,
ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene
glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanura- te, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7--
trioxabicyclo[2.2.2]octane.
[0271] 1.17. Amides of
13-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethyle-
nediamide,
N,N'-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)trimethyle-
nediamide,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,
N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxami-
de (Naugard.RTM.XL-1, supplied by Uniroyal).
[0272] 1.18. Ascorbic acid (vitamin C)
[0273] 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-phenyle- nediamine,
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-allyidiphenylamine, 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-butyl-aminophenol,
4-butyrylaminophenol, 4-nonanoylaminophenol,
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'-tetra-methyl-4,4'-diaminodiphenylmethane,
1,2-bis[(2-methylphenyl)a- mino]ethane,
1,2-bis(phenylamino)propane, (o-tolyl)biguamide,
bis[4-(1',3'-dimethylbutyl)phenyl]amine, tert-octylated
N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated
tert-butyl/tert-octyldiphenylamines, a mixture of mono- and
dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated
dodecyldiphenylamines, a mixture of mono- and dialkylated
isopropyl/isohexyldiphenylamines, a mixture of mono- and
dialkylated tert-butyldiphenylamines,
2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a
mixture of mono- and dialkylated tert-butyl/tert-octylph-
enothiazines, a mixture of mono- and dialkylated
tert-octylphenothiazines, N-allylphenothiazine,
N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene,
N,N-bis(2,2,6,6-tetramethylpiperid-4-yl-hexamethylenediamine,
bis(2,2,-6,6-tetramethylpiperid-4-yl)sebacate,
2,2,6,6-tetramethylpiperid- in-4-one,
2,2,6,6-tetramethylpiperidin-4-ol.
[0274] 2. UV absorbers and light stabilisers
[0275] 2.1.2-(2'-Hydroxyphenyl)benzotriazoles, for example
2-(2'-hydroxy-5'-methylphenyl)benzotriazole,
2-(3',5'-di-tert-butyl-2'-hy- droxyphenyl)benzotriazole,
2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole- ,
2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole,
2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,
2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole,
2-(3',5'-di-tert-amyl-2'-h- ydroxyphenyl)benzotriazole,
2-(3',5'-bis(.alpha.,.alpha.-dimethylbenzyl)-2-
'-hydroxyphenyl)benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxyc-
arbonylethyl)phenyl)-5-chlorobenzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethy-
lhexyloxy)carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobe-
nzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl-
)benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)ph-
enyl)benzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-
-2'-hydroxyphenyl)benzotriazole,
2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)- benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)-
phenylbenzotriazole,
2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benz-
otriazole-2-ylphenol]; the transesterification product of
2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotr-
iazole with polyethylene glycol 300;
[R--CH.sub.2CH.sub.2--COO--CH.sub.2CH- .sub.2.sub.2, where
R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphen- yl,
2-[2'-hydroxy-3'-(,sa-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)phe-
nyl]-benzotriazole;
2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(.alpha-
.,.alpha.-dimethylbenzyl)phenyl]benzotriazole.
[0276] 2.2.2-Hydroxybenzophenones, for example the 4-hydroxy,
4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy,
4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
[0277] 2.3. Esters of substituted and unsubstituted benzoic acids,
for example 4-tert-butylphenyl salicylate, phenyl salicylate,
octylphenyl salicylate, dibenzoyl resorcinol,
bis(4-tert-butylbenzoyl)resorcinol, benzoyl resorcinol,
2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybe- nzoate,
hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl
3,5-di-tert-butyl-4-hydroxybenzoate,
2-methyl-4,6-di-tert-butylphenyl
3,5-di-tert-butyl-4-hydroxybenzoate.
[0278] 2.4. Acrylates, 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-methoxycinnamate, methyl
.alpha.-carbomethoxy-p-methoxycinnamate and
N-(.beta.-carbomethoxy-.beta.- -cyanovinyl)-2-methylindoline.
[0279] 2.5. Nickel compounds, for example nickel complexes of
2,2'-thiobis[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-methylphenylunde- cylketoxime,
nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or
without additional ligands.
[0280] 2.6. Sterically hindered amines, for example
bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,
bis(2,2,6,6-tetramethyl-4-p- iperidyl)succinate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate,
bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate,
bis(1,2,2,6,6-pentamethyl-4-piperidyl)
n-butyl-3,5-di-tert-butyl-4-hydrox- ybenzylmalonate, the condensate
of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-- 4-hydroxypiperidine and
succinic acid, linear or cyclic condensates of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-tert-octylamino-2,6-di-chloro-1,3,5-triazine,
tris(2,2,6,6-tetramethyl-- 4-piperidyl)nitrilotriacetate,
tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1-
,2,3,4-butanetetracarboxylate,
1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetrameth- ylpiperazinone),
4-benzoyl-2,2,6,6-tetramethylpiperidine,
4-stearyloxy-2,2,6,6-tetramethylpiperidine,
bis(1,2,2,6,6-pentamethylpipe-
ridyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)-malonate,
3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate,
bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, linear or
cyclic condensates of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediam- ine and
4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of
2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triaz-
ine and 1,2-bis(3-aminopropylamino)-ethane, the condensate of
2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-tri-
azine and 1,2-bis(3-aminopropylamino)ethane,
8-acetyl-3-dodecyl-7,7,9,9-te-
tramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione,
3-dodecyl-1-(2,2,6,6-tet-
ramethyl-4-piperidyl)pyrrolidine-2,5-dione,
3-dodecyl-1-(1,2,2,6,6-pentame-
thyl-4-piperidyl)pyrrolidine-2,5-dione, a mixture of
4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, a
condensate of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of
1,2-bis(3-aminopropylamino)ethane and
2,4,6-trichloro-1,3,5-triazine as well as
4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.
(136504-96-6]); a condensate of 1,6-hexanediamine and
2,4,6-trichloro-1,3,5-triazine as well as N,N-dibutylamine and
4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.
[192268-64-7]);
N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,
N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,
2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane,
a reaction product of
7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4--
oxospiro-[4,5]decane and epichlorohydrin,
1,1-bis(1,2,2,6,6-pentamethyl-4--
piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene,
N,N'-bis-formyl-N,N'-bis(-
2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine, a diester of
4-methoxymethylenemalonic acid with
1,2,2,6,6-pentamethyl-4-hydroxypiperi- dine,
poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyi)]siloxane-
, a reaction product of maleic acid anhydride-a-olefin copolymer
with 2,2,6,6-tetramethyl-4-aminopiperidine or
1,2,2,6,6-pentamethyl-4-aminopip- eridine.
[0281] 2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide,
2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide,
2,2'-didodecyloxy-5,5'-di-tert-butoxanilide,
2-ethoxy-2'-ethyloxanilide, N,N'-bis(3-dimethylaminopropyl)oxamide,
2-ethoxy-5-tert-butyl-2'-ethoxani- lide and its mixture with
2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, mixtures of o- and
p-methoxy-disubstituted oxanilides and mixtures of o- and
p-ethoxy-disubstituted oxanilides.
[0282] 2.8.2-(2-Hydroxyphenyl)-1,3,5-triazines, 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-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazin-
e,
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazi-
ne,
2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-tr-
iazine,
2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-di-
methyl)-1,3,5-triazine,
2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phen-
yl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine,
2-[4-(dodecyloxy/tridecyloxy-2-h-
ydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-
,
2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimeth-
ylphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,- 5-triazine,
2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,
2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,
2-{2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,
2-(2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis-
(2,4-dimethylphenyl)-1,3,5-triazine.
[0283] 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.
[0284] 4. Phosphites and phosphonites, for example triphenyl
phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites,
tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl
phosphite, distearylpentaerythritol diphosphite,
tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol
diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol
diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite,
bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,
diisodecyloxypentaerythritol diphosphite,
bis(2,4-di-tert-butyl-6-methylp- henyl)-pentaerythritol
diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentae- rythritol
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-dioxaphosph-
ocin, bis(2,4-di-tertbutyl-6-methylphenyl)methyl phosphite,
bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite,
6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2-dioxaphosp-
hocin,
2,2',2"-nitrilo-[triethyltris(3,3',5,5'-tetra-tert-butyl-1,1'-biphe-
nyl-2,2'-diyl)phosphite],
2-ethylhexyl(3,3',5,5'-tetra-tert-butyl-1,1'-bip-
henyl-2,2'-diyl)phosphite,
5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-
-1,3,2-dioxaphosphirane.
[0285] The following phosphites are especially preferred:
[0286] Tris(2,4-di-tert-butylphenyl) phosphite (Irgafos.RTM.168,
Ciba-Geigy), tris(nonylphenyl) phosphite, 27
[0287] 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.
[0288] 6. Nitrones, for example N-benzyl-alpha-phenylnitrone,
N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptyinitrone,
N-lauryl-alpha-undecyinitrone, N-tetradecyl-alpha-tridecylnitrone,
N-hexadecyl-alpha-pentadecylnitrone,
N-octadecyl-alpha-heptadecyinitrone,
N-hexadecyl-alpha-heptadecyinitrone,
N-ocatadecyl-alpha-pentadecylnitrone- ,
N-heptadecyl-alpha-heptadecyinitrone,
N-octadecyl-alpha-hexadecylnitrone- , nitrone derived from
N,N-dialkylhydroxylamine derived from hydrogenated tallow
amine.
[0289] 7. Thiosynergists, for example dilauryl thiodipropionate or
distearyl thiodipropionate.
[0290] 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.
[0291] 9. Polyamide stabilisers, for example copper salts in
combination with iodides and/or phosphorus compounds and salts of
divalent manganese.
[0292] 10. Basic co-stabilisers, for example melamine,
polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea
derivatives, hydrazine derivatives, amines, polyamides,
polyurethanes, alkali metal salts and alkaline earth metal salts of
higher fatty acids, for example calcium stearate, zinc stearate,
magnesium behenate, magnesium stearate, sodium ricinoleate and
potassium palmitate, antimony pyrocatecholate or zinc
pyrocatecholate.
[0293] 11. Nucleating agents, for example inorganic substances,
such as talcum, metal oxides, such as titanium dioxide or magnesium
oxide, phosphates, carbonates or sulfates of, preferably, alkaline
earth metals; organic compounds, such as mono- or polycarboxylic
acids and the salts thereof, e.g. 4-tert-butylbenzoic acid, adipic
acid, diphenylacetic acid, sodium succinate or sodium benzoate;
polymeric compounds, such as ionic copolymers (ionomers).
Especially preferred are 1,3:2,4-bis(3',4'-dimethy-
lbenzylidene)sorbitol, 1,3:2,4-di(paramethyldibenzylidene)sorbitol,
and 1,3:2,4-di(benzylidene)sorbitol.
[0294] 12. Fillers and reinforcing agents, for example calcium
carbonate, silicates, glass fibres, glass bulbs, asbestos, talc,
kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon
black, graphite, wood flour and flours or fibers of other natural
products, synthetic fibers.
[0295] 13. Other additives, for example plasticisers, lubricants,
emulsifiers, pigments, rheology additives, catalysts, flow-control
agents, optical brighteners, flameproofing agents, antistatic
agents and blowing agents.
[0296] 14. 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-butylbenzofuran-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-butylbenzofuran-2-one,
3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one,
3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,
3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one.
[0297] The weight ratio of the compounds of this invention to the
conventional additives may be for example 1:0.5 to 1:5.
[0298] Other materials which may be stabilized with the compounds
of the formula (IA) or (IB) are recording materials for
photographic reproduction and other reprographic techniques as
described for example in Research Disclosure 1990, 31429 (pages
474-480), GB-A-2,319,523 or DE-A-19,750,906, page 22, line 15 to
page 105, line 32.
[0299] Thus, another preferred embodiment of this invention is a
recording material, in particular a photographic material,
containing at least one compound of the formula (IA) or (IB) with
the proviso being not applied to the definition of the formula
(IA).
[0300] Of special importance is also the stabilization of
non-silver reprographic materials, for example, those used for
pressure-sensitive copying systems, microcapsule photocopier
systems, heat-sensitive copier systems and ink-jet printing.
[0301] The recording materials stabilized with the compounds of the
formula (IA) or (IB) have an unexpectedly high quality, especially
in terms of their light stability.
[0302] The recording materials have a structure which is known per
se and which corresponds to their utility. They consist of a base,
for example a paper or plastic film, on which one or more coatings
are applied. Depending on the type of the material, these coats
contain the suitable components required. In the case of
photographic materials, the coats contain for example silver halide
emulsions, colour couplers, dyes and the like. The material
intended for ink-jet printing has e.g. a customary base on which an
absorption layer suitable for ink is located. Uncoated paper can
likewise be employed for ink-jet printing. In the latter case, the
paper simultaneously functions as a base and has the absorbent for
the ink. Suitable materials for ink-jet printing are described,
inter alia, in U.S. Pat. No. 5,073,448, the disclosure content of
which is regarded as part of the present description.
[0303] The recording material can also be transparent, for example
in the case of projection films.
[0304] The compound of the formula (IA) or (IB) can be incorporated
into the material even in the course of manufacture; in
papermaking, for example, by addition to the pulp. Another method
of use is the spraying of the material with an aqueous solution of
the compound of the formula (IA) or (IB), or the addition thereof
to the coating.
[0305] Coatings for transparent recording materials for projection
must not contain any light-scattering particles such as pigments or
fillers.
[0306] The colour-binding coatings can contain further additives,
for example antioxidants, light stabilizers (including UV absorbers
and/or conventional hindered amine light stabilizers), viscosity
improvers, brighteners, biocides and/or antistats.
[0307] The coating is usually prepared as described in the
following. The water-soluble components, for example the binder,
are dissolved in water and mixed. The solid components, for example
fillers and other additives as already described, are dispersed in
this aqueous medium. Dispersion is advantageously brought about
with the aid of equipment such as ultrasonic devices, turbine
agitators, homogenizers, colloid mills, bead mills, sand mills,
high-speed stirrers and the like. A particular advantage of the
compounds of the formula (IA) or (IB) is that they can easily be
incorporated into the coating.
[0308] As mentioned above, the recording materials cover a broad
field of use. Compounds of the formula (IA) or (IB) can be
employed, for example, in pressure-sensitive copier systems. They
can be added to the paper to protect the micro-encapsulated dye
precursors against light, or to the binder of the developer layer
for protecting the dyes formed therein.
[0309] Photocopier systems with light-sensitive microcapsules which
are developed by pressure are described, inter alia, in U.S. Pat.
No. 4,416,966, U.S. Pat. No. 4,483,912, U.S. Pat. No. 4,352,200,
U.S. Pat. No. 4,535,050, U.S. Pat. No. 4,536,463, U.S. Pat. No.
4,551,407, U.S. Pat. No. 4,562,137 and U.S. Pat. No. 4,608,330 and
also in EP-A-139,479, EP-A-162,664, EP-A-164,931, EP-A-237,024,
EP-A-237,025 and EP-A-260,129. In all these systems, the compounds
of the formula (IA) or (IB) can be added to the colour-accepting
layer. Alternatively, the compounds of the formula (IA) or (IB) can
be added to the donor layer for protecting the colour formers
against light.
[0310] The compounds of the formula (IA) or (IB) can also be
employed in recording materials which are based on the principle of
photopolymerization, photosoftening or the rupture of
microcapsules, or, when heat-sensitive or photosensitive diazonium
salts, leuco dyes with oxidizing agent or colour lactones with
Lewis acids are used.
[0311] Heat-sensitive recording material exploits the
colour-imparting reaction between a colourless or weakly coloured
base dye and an organic or inorganic colour developer; the recorded
image being produced by heat-induced contact of the two materials.
This type of heat-sensitive recording material is very widespread,
not only as the recording medium for faxes, computers, etc., but
also in many other fields, for example in label printing.
[0312] The heat-sensitive recording material according to the
present invention is composed of a base, a heat-sensitive
colour-forming recording layer on this base, and, optionally, a
protective layer on the heat-sensitive, colour-forming recording
layer. The heat-sensitive, colour-forming recording layer contains
as its principal constituent a colour-imparting compound and a
colour-developing compound, and also a compound of the formula (IA)
or (IB). If a protective layer is present, the compound of the
formula (IA) or (IB) can also be incorporated into the protective
layer.
[0313] Heat-sensitive recording materials are described, for
example, in JP-A-Hei 8-267 915.
[0314] Further fields of use are recording materials for dye
diffusion transfer printing, thermal wax transfer printing and dot
matrix printing, and for use with electrostatic, electrographic,
electrophoretic, magnetographic and laser-electrophotographic
printers, recorders or plotters. Of the materials mentioned,
preference is given to recording materials for dye diffusion
transfer printing as described for example in EP-A-507,734.
[0315] Compounds of the formula (IA) or (IB) can also be employed
in inks (preferably for ink-jet printing) for example as described
in U.S. Pat. No. 5,098,477, the disclosure content of which is
regarded as part of the present description. The invention
therefore preferably also relates to an ink comprising at least one
compound of the formula (IA) or (IB) as stabilizer. The ink,
especially for ink-jet printing, contains preferably water. Inks
contain the stabilizer of the formula (IA) or (IB) usually in a
concentration of from 0.01 to 20% by weight, in particular from 0.5
to 10% by weight.
[0316] The photographic material according to this invention can be
a black and white or can be a colour photographic material. A
colour photographic material is preferred.
[0317] Examples of colour photographic materials are colour
negative films, colour reversal films, colour positive films,
colour photographic paper, colour reversal photographic paper,
colour-sensitive materials for the dye diffusion transfer process
or the silver dye bleach process.
[0318] Details of the photographic materials to be stabilized
according to this invention and components which can be employed
therein are given, inter alia, in GB-A-2,319,523, DE-A-19,750,906,
page 23, line 20 to page 105, line 32, and U.S. Pat. No. 5,538,840,
column 25, line 60 to column 106, line 31. These parts of U.S. Pat.
No. 5,538,840 are incorporated herein by way of reference.
[0319] The compounds of this invention can be introduced in any
layer of a silver halide photographic material, however, they are
preferably incorporated in a chromogenic layer, in particular in a
layer containing a yellow coupler. They are used, for example, in a
1% to 200% weight ratio with the coupler, preferably 1% to 100%.
The compounds of the present invention can be used in combination
with other conventional stabilizers that can be incorporated in the
same layer or in a different layer. Examples of suitable
conventional stabilizers are described in GB-A-2,319,523,
DE-A-19,750,906 and U.S. Pat. No. 5,538,840 and include in
particular phenolic stabilizers, conventional hindered amine
stabilzers, UV absorbers, preferably those of the hydroxyphenyl
benztriazole type or of the hydroxyphenyl triazine class, and the
like.
[0320] Examples of yellow couplers are also disclosed in U.S. Pat.
No. 5,538,840, column 33, line 3 to column 47, line 15.
[0321] Thus, further preferred embodiments of this invention
are:
[0322] (1) A photographic material comprising on a substrate at
least one layer containing a compound of the formula (IA) or
(IB).
[0323] (2) A silver halide colour photographic material comprising
a support having thereon at least one light-sensitive silver halide
emulsion layer and optionally a non-light sensitive emulsion layer,
characterized in that at least one light-sensitive layer contains a
compound of the formula (IA) or (IB).
[0324] (3) A silver halide colour photographic material comprising
a support having thereon a) at least one cyan-forming unit composed
of a red-sensitive silver halide emulsion layer containing a cyan
dye-forming coupler, b) at least one magenta-forming unit composed
of a green-sensitive silver halide emulsion layer containing a
magenta dye-forming coupler and c) at least one yellow-forming unit
composed of a blue-sensitive silver halide emulsion layer
containing a yellow dye-forming coupler, characterized in that
[0325] the blue-sensitive layer contains a compound of the formula
(IA) or (IB).
[0326] The invention is illustrated in more detail by the following
Examples. All percentages are by weight, unless otherwise
indicated.
EXAMPLE 1
Preparation of the Compound of the Formula
[0327] 28
[0328] 1.1. Preparation of the Intermediate
2,2,5,5-tetramethylimidazolidi- ne-4-thione:
[0329] 525 ml of water, 143 g of NH.sub.4Cl and 106.7 g of
Na.sub.2S are placed in a 2 l four necked flask equipped with a
mechanical stirrer, thermometer, condenser and gas inlet tube. The
solution is stirred for 30 minutes and 102 g of acetone are added.
During 2 hours at 20/25.degree. C., 85 g of acetone cyanohydrin are
added dropwise to the solution obtained. The mixture is left to
react under stirring for additional 2 hours. The suspension
obtained is heated to 60.degree. C. and is stirred for additional 2
hours. Then, the suspension is heated to 85.degree. C. and NH.sub.3
is removed. The reaction mixture is cooled to 20.degree. C. and a
white solid is recovered, washed with 200 ml of water and dried at
30.degree. C. under vacuum.
[0330] 1.2. Preparation of the Intermediate
2,2,5,5-tetramethylimidazolidi- ne-4-one:
[0331] 290 g (1.83 mol) of the intermediate of step 1.1 are
dissolved in water. Then, 183 g of NaOH are added. The solution is
cooled to 5.degree. C. and 893 g of a water solution of 35% (w/w)
of H.sub.2O.sub.2 is slowly added. After adding, the mixture is
heated at room temperature. The solution pH is corrected to 8 with
acetic acid and the water is removed. Then, 1 l of dichloromethane
is added and the salts are filtered off. The organic solution is
dried under anhydrous sodium sulphate and evaporated under
vacuum.
[0332] 1.3. Preparation of the Intermediate of the Formula 29
[0333] 132 g (1.16 mol) of potassium tert-butoxide are slowly added
to a suspension of 168 g (1.18 mol) of the intermediate of step 1.2
in 500 ml of anhydrous toluene. After the addition, 131 g (0.54
mol) of 1.6-dibromohexane are added. The mixture is left to react
for 4 hours and then washed twice with water. The organic layer is
dried under anhydrous sodium sulphate and then evaporated under
vacuum.
[0334] 1.4. Preparation of the Intermediate of the Formula 30
[0335] A mixture of 138 g (0.38 mol) of the intermediate of step
1.3, 121.5 g (1 mol) of allyl bromide and 140 g (1 mol) of
potassium carbonate in 500 ml of toluene is poured into an
autoclave. The mixture is heated at 145.degree. C. for 10 hours.
Then, the mixture is washed twice with 250 ml of water, the organic
layer is separated, dried under sodium sulphate and evaporated
under vacuum. The product obtained is a yellow powder with a visual
melting range of 82-87.degree. C.
[0336] 1.5. Preparation of the Final Product:
[0337] The mixture of 44 g (0.099 mol) of the intermediate of step
1.4 and 130 g (1.24 mol) of sodium carbonate in 150 ml of toluene
is cooled at -5.degree. C. and a solution of 35% (w/w) of
per-acetic acid in acetic acid (23 g, 0.30 mol) is slowly added.
After the addition, the mixture is left to react for additional 2
hours at -5.degree. C. and then additional 30 hours at room
temperature. Subsequently, the mixture is washed twice with 50 ml
of water, the organic layer is separated, dried under sodium
sulphate and evaporated under vacuum. A pale yellow oil is
obtained.
[0338] .sup.1H NMR (300 MHz, CDCl.sub.3): .delta. 5.84-5.73 (m,
2H); 5.15-5.02 (m, 4H); 4.18-4.16 (m, 4H); 2.99 (t, 4H); 1.44-1.37
(m, 8H); 1.13 (s, 12H); 1.06-1.01 (s, 12H).
EXAMPLE 2
Preparation of the Compound of the Formula
[0339] 31
[0340] 0.5 g of Pt on carbon (5% w/w) are added to a solution of 30
g (0.063 mol) of the compound of EXAMPLE 1 in 120 ml of methanol.
Then, the mixture is poured into an autoclave and hydrogenated for
4 hours at 20 bar (H.sub.2 pressure) and 30.degree. C. The mixture
is filtered off and the solution is concentrated under vacuum. The
product obtained is a yellow powder with a visual melting range of
60-67.degree. C.
EXAMPLE 3
Preparation of the Compound of the Formula
[0341] 32
[0342] 3.1. Preparation of the Intermediate of the Formula 33
[0343] 341 g (4.1 mol) of sodium carbonate and 433 g (13.53 mol) of
methanol are added dropwise to a suspension of 250 g (1.35 mol) of
cyanuric chloride in 500 ml of xylene. The mixture is left to react
at 35.degree. C. for about 70 hours. Then, the mixture is filtered
off to eliminate the salts and the solution is evaporated under
vacuum. The row material is crystallized from n-octane.
[0344] 3.2. Preparation of the Final Product:
[0345] 41 g (0.35 mol) of potassium tert-butoxide are slowly added
to a suspension of 55 g (0.39 mol) of the intermediate of EXAMPLE
1, step 1.2 in 200 ml of toluene. After the addition, the mixture
is left to react at 40.degree. C. for about 1 hour. Vacuum is
inserted and always at 40.degree. C. 100 ml of solution are
distilled off. Then, the solution is cooled to 20.degree. C., 100
ml of toluene are added again and 62 g (0.35 mol) of the
intermediate of EXAMPLE 1, step 1.2 are slowly added. After the
addition, the mixture is left to react for additional 2 hours and
then 40 ml of water are added. The organic layer is separated,
washed twice with water, dried on anhydrous sodium sulphate, and
evaporated under vacuum. The raw material is crystallized from a
mixture of 35 ml of toluene and 35 ml of n-octane. The product
obtained is a white powder with a visual melting range of
80-88.degree. C.
EXAMPLE 4
Preparation of the Compound of the Formula
[0346] 34
[0347] 4.1. Preparation of the Intermediate of the Formula 35
[0348] 34.16 g (0.74 mol) of formic acid are slowly added to a
suspension of 70 g (0.44 mol) of the compound of EXAMPLE 1, step
1.2 in 100 ml of tert-amyl alcohol. The temperature is increased to
60.degree. C. and 8.5 g of formic aldehyde are added. The mixture
is left to react for one hour at 75.degree. C. and then, further
8.5 g of formic aldehyde are added. The mixture reacts for
additional three hours. After cooling, 300 ml of dichloromethane
are added and after half an hour the organic layer is separated,
washed twice with water, dried over anhydrous sodium sulphate and
evaporated under vacuum. The raw material is purified by
crystallization from n-hexane. A white solid is obtained.
[0349] 4.2. Preparation of the Final Product:
[0350] Following the procedure reported in EXAMPLE 3, step 3.2 and
using as starting material the intermediate of step 1, the final
product is obtained as a white powder with a visual melting 3 range
of 81-87.degree. C.
EXAMPLE 5
Preparation of the Compound of the Formula
[0351] 36
[0352] 5.1. Preparation of the Intermediate of the Formula 37
[0353] A solution of 75 g (0.41 mol) of cyanuric chloride in 250 ml
of THF (tetrahydrofuran) is slowly added to a mixture of 45 g (0.61
mol) of n-butanol and 50 g (0.59 mol) of sodium carbonate in 100 ml
of THF. The mixture is left to react overnight at 40.degree. C.
Then, it is filtered on clay in order to eliminate the salts. The
organic solution is evaporated under vacuum.
[0354] 5.2. Preparation of the Final Product:
[0355] Following the procedure described in EXAMPLE 3, step 3.2 and
using as starting materials the intermediates of EXAMPLE 4 step 4.1
and EXAMPLE 5, step 5.1, the final product is obtained as a white
powder with a visual melting range of 121-128.degree. C.
EXAMPLE 6
Preparation of the Compound of the Formula
[0356] 38
[0357] 6.1. Preparation of the Intermediate of the Formula 39
[0358] Following the procedure described in EXAMPLE 5, step 5.1 and
using iso-propanol as starting material, a pale yellow oil is
obtained.
[0359] 6.2. Preparation of the Final Product:
[0360] Following the procedure described in EXAMPLE 3, step 3.2 and
using as starting materials the intermediates of EXAMPLE 1, step
1.2 and EXAMPLE 6, step 6.1, the final product is obtained as a
white powder with a visual melting range of 181-186.degree. C.
[0361] Compounds of the Formula (IA) or (IB) used as Stabilizers in
the Following Application Examples: 40 41 42 43 44
EXAMPLE A-1
Stabilization of a Red Pigmented and Sulfur Crosslinked
ethylene-propylene-diene-elastomer (EPDM)
[0362]
1 Recipe in parts by weight: EPDM (Buna .RTM. AP 451) 100.0 Silica
(Ultrasil .RTM. VN 3) 30.0 Paraffin oil (Naftolen .RTM. ND) 20.0
Stearic acid 1.0 ZnO 3.0 Carbowax 2.0 TiO.sub.2 2.0
4,6-Bis{octylthiomethyl}-o-cresol 0.5 Sulfur 1.5 Vulkacit .RTM.
CZ/C 1.0 Vulkacit .RTM. Thiuram MS 0.8 Pigment Microlen .RTM. Red
MO 3302 0.5 Light Stabilizer (see Table A-1) 1.0
[0363] The components of the recipe are mixed at 70.degree. C. in
an open roll mill. For incorporation of the pigment, the
temperature is raised to 110C. The cure time at 160.degree. C. is
determined in a MDR 2000 rheometer.
[0364] 2 mm plates are cured at 160.degree. C. until t.sub.95 of
the rheometer curve (minutes to 95% of the rheometer curve
maximum).
[0365] The rubber samples are exposed to artificial light in an
ATLAS.RTM. Cl 1200 Weather-O-meter without water spray. The
.DELTA.E is periodically determined according to ASTM D 1925-70.
The results are indicated in Table A-1.
2 TABLE A-1 Light Stabilizer .DELTA.E after 1000 hours *) Without
11 Stabilizer 1 7.4 *) Low values are desired.
EXAMPLE A-2
Stabilization of a Green Pigmented and Sulfur Crosslinked
ethylene-propylene-diene-elastomer (EPDM)
[0366]
3 Recipe in parts by weight: EPDM (Buna .RTM. AP 451) 100.0 Silica
(Ultrasil .RTM. VN 3) 30.0 Paraffin oil (Ingraplast .RTM. SRSS)
20.0 Stearic acid 1.0 ZnO 3.0 Carbowax 2.0 TiO.sub.2 2.0
4,6-Bis{octylthiomethyl}-o-cresol 0.5 Sulfur 1.5 Vulkacit .RTM.
CZ/C 1.0 Vulkacit .RTM. Thiuram MS 0.8 Pigment Microlen .RTM. Green
MO 177 0.5 Light Stabilizer (see Table A-2) 1.0
[0367] The components of the recipe are mixed at 70.degree. C. in
an open roll mill. For incorporation of the pigment, the
temperature is raised to 110.degree. C. The cure time at
160.degree. C. is determined in a MDR 2000 rheometer.
[0368] 2 mm plates are cured at 160.degree. C. until T.sub.95 of
the rheometer curve (minutes to 95% of the rheometer curve
maximum).
[0369] The rubber samples are exposed to artificial light in an
ATLAS.RTM. Cl 1200 Weather-O-meter without water spray. The AE is
periodically determined according to ASTM D 1925-70. The results
are indicated in Table A-2.
4 TABLE A-2 Light Stabilizer .DELTA.E after 1000 hours *) Without
20 Stabilizer 1 7.4 Stabilizer 2 11 *) Low values are desired.
EXAMPLE A-3
Stabilization of a Yellow Pigmented and Sulphur Crosslinked
styrene-butadiene-copolymer (SBR)
[0370]
5 Recipe in parts by weight: .RTM. ESBR 1709 (.RTM. Enichem) 100.0
ZnO 5.0 Stearic acid 1.0 .RTM. Winnofil/ICI (white filler) 50.0
Pigment .RTM. Microlene Yellow MOO 138 3G 0.5 TIO.sub.2 (Rutile)
3.0 Sulphur 2.0 .RTM. Vulkacit DM (.RTM. Bayer) 1.5 .RTM. Vulkacit
D (.RTM. Bayer) 0.5 Light Stabilizer (see Table A-3) 1.6
[0371] The components of the recipe and the stabilizer listed in
Table A-3 are mixed at 70.degree. C. in an open roll mill. For
incorporation of the pigment, the temperature is raised to
110.degree. C.
[0372] The cure time at 130.degree. C. is determined in a MDR 2000
rheometer.
[0373] 2 mm plates are cured at 130.degree. C. until T.sub.95 of
the rheometer curve (minutes to 95% of the rheometer curve
maximum).
[0374] The rubber samples are exposed to artificial light in an
.RTM.Atlas Cl 1200 Weather-O-meter without water spray. The
Yellowness-Index (.DELTA.L and .DELTA.a) is determined periodically
according to ASTM D 1925-70. The results are indicated in Table
A-3.
6 TABLE A-3 Light Stabilizer .DELTA.L after 500 hours .DELTA.a
after 500 hours Without -11 11.6 Stabilizer 3 -8 9.2 Stabilizer 4
-4 6.1
EXAMPLE B-1
Stabilization of Photographic Layers
[0375] Chromogenic photographic layers are prepared by coating a
gelatine emulsion containing silver bromide, a yellow coupler and
an additive on a polyethylene-coated paper.
[0376] The composition of the layers is as given in the following
table (all amounts in mg/m.sup.2):
7 Component Amount in the layer Gelatine 5150 AgBr 520 Yellow
coupler Coup Y1 769 Coupler solvent Solv1 256 Additive (Table B-1)
231 Hardener Ha1 300 Surfactant Su1 340
[0377] The layers are dried for 7 days in a ventilated cabinet.
[0378] The dried samples are exposed to white light through a step
wedge of 0.3 log E exposure steps and then developed with Agfa's
P94 process for colour negative papers, following manufacturer's
recommendations.
[0379] After exposure and processing, the remission density of the
yellow dye is measured in the blue channel. The samples are then
exposed in an Atlas Weatherometer so as to receive 60 kJ/cm.sup.2
light energy. The temperature is 43.degree. C. and the relative
humidity 50%. The density loss starting from a density of 1 is
determined.
8 TABLE B-1 Density loss (%) Additive (initial density = 1) None 46
Stabilizer 5 17
[0380] The above table shows that Stabilizer 5 according to the
present invention improves the light stability of the yellow dye.
45
EXAMPLE C-1
Stabilization of Polypropylene Blue Plaques
[0381] 1 g of Stabilizer 2 (solubilized in the minimum amount of
acetone), 1 g of calcium stearate and 1 g of Blue .RTM.Filofin G
are mixed in a turbomixer with 1000 g of polypropylene .RTM.Montell
JE 6100 powder which contains 835 ppm of
tris(2,4-di-tert-butylphenyl) phosphite and 355 ppm of
pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4-hydroxyphenyl)
propionate) and which has a melt index of 3 g/10 min (measured at
230.degree. C. and 2.16 Kg).
[0382] The mixture is extruded at a maximum temperature of
230.degree. C. using a .RTM.Berstoff extruder, to give polymer
granules, which are subsequently converted to plaques 2 mm thick,
using an injection molding machine .RTM.Negri-Bossi, Italy) and
working at a maximum temperature of 220.degree. C.
[0383] The plaques thus prepared are mounted on a white card and
exposed in a Weather-O-Meter .RTM.Atlas Ci65A (ASTM G26, continuous
exposure to light without water spray) with a black panel
temperature of 63.degree. C. and relative humidity of 30%.
[0384] The degree of chalking and superficial roughness are
measured, as an evaluation of surface degradation, on samples taken
after various light exposure times. A numeric scale, where 10 is
the top value for the non exposed (not degraded) sample is adopted
to rank the degree of chalking of the samples. Roughness is
measured with a "Surtronic 3+".
[0385] By way of comparison, a plaque prepared under the same
conditions as indicated above, but without the addition of the
stabilizer of the present invention, is exposed.
[0386] The results obtained are shown in Table 1.
9TABLE 1 *) Hours of *) Hours of Weather-O-Meter Weather-O-Meter
exposure Stabilizer exposure to chalking to 0.50 .mu.m roughness --
600 348 Stabilizer 2 2600 2678 *) High numbers are desired.
* * * * *