U.S. patent application number 10/572154 was filed with the patent office on 2007-03-22 for stabilization of photochromic systems.
Invention is credited to Mara Destro, Dario Lazzari, Dirk Simon, Manuele Vitali.
Application Number | 20070064195 10/572154 |
Document ID | / |
Family ID | 34384662 |
Filed Date | 2007-03-22 |
United States Patent
Application |
20070064195 |
Kind Code |
A1 |
Destro; Mara ; et
al. |
March 22, 2007 |
Stabilization of photochromic systems
Abstract
Photochromic compositions are disclosed comprising a polymeric
material, a photochromic dye, a hydroxyphenyl triazine UV absorber
and, optionally, a further light stabilizer selected from the
sterically hindered amines. These systems provide a reversible
photochromic effect and show improved light stabilization and color
fastness.
Inventors: |
Destro; Mara; (Bologna,
IT) ; Lazzari; Dario; (Bologna, IT) ; Simon;
Dirk; (Lorrach-Brombach, DE) ; Vitali; Manuele;
(Bologna, IT) |
Correspondence
Address: |
CIBA SPECIALTY CHEMICALS CORPORATION;PATENT DEPARTMENT
540 WHITE PLAINS RD
P O BOX 2005
TARRYTOWN
NY
10591-9005
US
|
Family ID: |
34384662 |
Appl. No.: |
10/572154 |
Filed: |
September 20, 2004 |
PCT Filed: |
September 20, 2004 |
PCT NO: |
PCT/EP04/52238 |
371 Date: |
March 16, 2006 |
Current U.S.
Class: |
351/63 ; 524/100;
524/91; 524/95 |
Current CPC
Class: |
C08K 5/3492
20130101 |
Class at
Publication: |
351/063 ;
524/091; 524/095; 524/100 |
International
Class: |
G02C 7/10 20060101
G02C007/10; C08K 5/3412 20060101 C08K005/3412; C08K 5/3477 20060101
C08K005/3477 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 29, 2003 |
EP |
03103587.6 |
Claims
1. Photochromic composition comprising a) a polymeric material, b)
a photochromic dye and c) a hydroxyphenyl triazine UV absorber (i)
conforming to formula I, II, III, IV, V or (100) ##STR70## wherein
Y is phenyl, naphthyl, or said phenyl or said naphthyl substituted
by one to three alkyl of 1 to 6 carbon atoms, by halogen, by
hydroxy or by alkoxy of 1 to 6 carbon atoms or by mixtures thereof;
or Y is Z.sub.1 or Z.sub.2; X is Z.sub.1 or Z.sub.2; R.sub.1 is
hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms,
cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon
atoms, halogen, --SR.sub.3, --SOR.sub.3 or --SO.sub.2R.sub.3; or
said alkyl, said cycloalkyl or said phenylalkyl substituted by one
to three halogen, --R.sub.4, --OR.sub.5, --N(R.sub.5).sub.2,
--COR.sub.5, --COOR.sub.5, --OCOR.sub.5, --CN, --NO.sub.2,
--SR.sub.5, --SOR.sub.5, --SO.sub.2R.sub.5 or
--P(O)(OR.sub.5).sub.2, morpholinyl, piperidinyl,
2,2,6,6-tetramethylpiperidinyl, piperazinyl or N-methylpiperidinyl
groups or combinations thereof; or said alkyl or said cycloalkyl
interrupted by one to four phenylene, --O--, --NR.sub.5--,
--CONR.sub.5--, --COO--, --OCO--or --CO groups or combinations
thereof; or said alkyl or said cycloalkyl both substituted and
interrupted by combinations of the groups mentioned above; R.sub.3
is alkyl of 1 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms,
cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon
atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by one
or two alkyl of 1 to 4 carbon atoms; R.sub.4 is aryl of 6 to 10
carbon atoms or said aryl substituted by one to three halogen,
alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or
combinations thereof; cycloalkyl of 5 to 12 carbon atoms;
phenylalkyl of 7 to 15 carbon atoms or said phenylalkyl substituted
on the phenyl ring by one to three halogen, alkyl of 1 to 8 carbon
atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof; or
straight or branched chain alkenyl of 2 to 18 carbon atoms; R.sub.5
is defined as is R.sub.4; or R.sub.5 is also hydrogen or straight
or branched chain alkyl of 1 to 24 carbon atoms, alkenyl of 2 to 24
carbon atoms; or R.sub.5 is a group for formula ##STR71## T is
hydrogen, oxyl, hydroxyl, --OT.sub.1, alkyl of 1 to 24 carbon
atoms, said alkyl substituted by one to three hydroxy; benzyl or
alkanoyl of 2 to 18 carbon atoms; T.sub.1 is alkyl of 1 to 24
carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkenyl of 2 to
24 carbon atoms, cycloalkenyl of 5 to 12 carbon atoms, phenylalkyl
of 7 to 15 carbon atoms, a radical of a saturated or unsaturated
bicyclic or tricyclic hydrocarbon of 7 to 12 carbon atoms or aryl
of 6 o 10 carbon atoms or said aryl substituted by one to three
alkyl of 1 to 4 carbon atoms; R.sub.2 is hydrogen, straight or
branched chain alkyl of 1 to 24 carbon atoms or cycloalkyl of 5 to
12 carbon atoms; or said alkyl or said cycloalkyl substituted by
one to four halogen, epoxy, glycidyloxy, furyloxy, --R.sub.4,
--OR.sub.5, --N(R.sub.5).sub.2, --CON(R.sub.5).sub.2, --COR.sub.5,
--COOR.sub.5, --OCOR.sub.5, --OCOC(R.sub.5).dbd.C(R.sub.5).sub.2,
--C(R.sub.5).dbd.CCOOR.sub.5, --CN, --NCO, or ##STR72## or
combinations thereof; or said alkyl or said cycloalkyl interrupted
by one to four epoxy, --O--, --NR.sub.5--, --CONR.sub.5--, --COO--,
--OCO--, --CO--, --C(R.sub.5).dbd.C(R.sub.5)COO--,
--OCOC(R.sub.5).dbd.C(R.sub.5)--, --C(R.sub.5).dbd.C(R.sub.5)--,
phenylene or phenylene-G-phenylene in which G is --O--, --S--,
--SO.sub.2--, --CH.sub.2-- or --C(CH.sub.3).sub.2-- or combinations
thereof, or said alkyl or said cycloalkyl both substituted and
interrupted by combinations of the groups mentioned above; or
R.sub.2 is --SO.sub.2R.sub.3 or --COR.sub.6; R.sub.6 is straight or
branched chain alkyl of 1 to 18 carbon atoms, straight or branched
chain alkenyl of 2 to 12 carbon atoms, phenoxy, alkylamino of 1 to
12 carbon atoms, arylamino of 6 to 12 carbon atoms, --R.sub.7COOH
or --NH--R.sub.8--NCO; R.sub.7 is alkylene of 2 to 14 carbon atoms
or phenylene; R8 is alkylene of 2 to 24 carbon atoms, phenylene,
tolylene, diphenylmethane or a group ##STR73## R.sub.1 and R.sub.1'
are the same or different and are as defined for R.sub.1; R.sub.2
and R.sub.2' are the same or different and are as defined for
R.sub.2; X and X' are the same or different and are as defined for
X; Y and Y' are the same or different and are as defined for Y; t
is 0 to 9; L is straight or branched alkylene of 1 to 12 carbon
atoms, cycloalkylene of 5 to 12 carbon atoms or alkylene
substituted or interrupted by cyclohexylene or phenylene; or L is
benzylidene; or L is --S--, --S--S--, --S--E--S--, --SO--,
--SO.sub.2--, --SO--E--SO--, --SO.sub.2--E--SO.sub.2--,
--CH.sub.2--NH--E--NH--CH.sub.2-- or ##STR74## E is alkylene of 2
to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms or
alkylene interrupted or terminated by cycloalkylene of 5 to 12
carbon atoms; n is 2, 3 or 4; when n is 2; Q is straight or
branched alkylene of 2 to 16 carbon atoms; or said alkylene
substituted by one to three hydroxy groups; or said alkylene
interrupted by one to three --CH.dbd.CH-- or --O--; or said
alkylene both substituted and interrupted by combinations of the
groups mentioned above; or Q is xylylene or a group
--CONH--R.sub.8--NHCO--,
--CH.sub.2CH(OH)CH.sub.2O--R.sub.9--OCH.sub.2CH(OH)CH.sub.2--,
--CO--R.sub.10--CO--, or
--(CH.sub.2).sub.m--COO--R.sub.11--OOC--(CH.sub.2).sub.m--, where m
is 1 to 3; or Q is ##STR75## R.sub.9 is alkylene of 2 to 50 carbon
atoms; or said alkylene interrupted by one to ten --O--, phenylene
or a group -phenylene-G-phenylene in which G is --O--, --S--,
--SO.sub.2--, --CH.sub.2-- or --C(CH.sub.3).sub.2--; R.sub.10 is
alkylene of 2 to 10 carbon atoms; or said alkylene interrupted by
one to four --O--, --S-- or --CH.dbd.CH--; or R.sub.10 is arylene
of 6 to 12 carbon atoms; R.sub.11 is alkylene of 2 to 20 carbon
atoms; or said alkylene interrupted by one to eight --O--; when n
is 3, Q is a group --[(CH.sub.2).sub.mCOO].sub.3--R.sub.12 where m
is 1 to 3, and R.sub.12 is an alkanetriyl of 3 to 12 carbon atoms;
when n is 4, Q is a group --[(CH.sub.2).sub.mCOO].sub.4--R.sub.13
where m is 1 to 3, and R.sub.14 is an alkanetetrayl of 4 to 12
carbon atoms; Z.sub.1 is a group of formula ##STR76## Z.sub.2 is a
group of formula ##STR77## where r.sub.1 and r.sub.2 are 1;
R.sub.14, R.sub.15, R.sub.16, R.sub.17, R.sub.18, R.sub.19,
R.sub.20, R.sub.21, R.sub.22 and R.sub.23 are independently of one
another hydrogen, hydroxy, cyano, alkyl of 1 to 20 carbon atoms,
alkoxy of 1 to 20 carbon atoms, phenylalkyl of 7 to 15 carbon
atoms, cycloalkyl of 5 to 12 carbon atoms, cycloalkoxy of 5 to 12
carbon atoms, halogen, haloalkyl of 1 to 5 carbon atoms, sulfo,
carboxy, acylamino of 2 to 12 carbon atoms, acyloxy of 2 to 12
carbon atoms, alkoxycarbonyl of 2 to 12 carbon atoms or
aminocarbonyl; or R.sub.17 and R.sub.18 or R.sub.22 and R.sub.23
together with the phenyl radical to which they are attached are a
cyclic radical interrupted by one to three --O-- or --NR.sub.5--;
x.sub.2 is a number from 1 to 50; A.sub.1 is a group of the formula
(101) ##STR78## or has one of the meanings given for T.sub.10;
D.sub.1 is C.sub.4-C.sub.12 alkylene or said alkylene substituted
by OH or interrupted by O or both substituted by OH and interrupted
by O; L.sub.1 is C.sub.1-C.sub.18alkylene;
C.sub.5-C.sub.12cycloalkylene; C.sub.3-C.sub.18alkenylene; or one
of said residues substituted by phenyl,
C.sub.7-C.sub.11alkylphenyl, C.sub.5-C.sub.12cycloalkyl, OH,
halogen, C.sub.1-C.sub.18alkoxy, C.sub.5-C.sub.12cycloalkoxy,
C.sub.3-C.sub.18alkenyloxy, COOH; the R.sub.50 are independently of
each other H, OR.sub.54 or OH, with the proviso that at least one
of R.sub.50 or R.sub.53 is OH; the R.sub.54 are independently of
each other hydrogen, C.sub.1-C.sub.12alkyl or a radical of formula
--L.sub.1--CO--O--R.sub.55; R.sub.55 is H, C.sub.1-C.sub.18alkyl,
C.sub.2-C.sub.12hydroxyalkyl; R.sub.51 is hydrogen,
C.sub.1-C.sub.4alkyl, Cl, phenyl or a group --OR.sub.54; R.sub.52
is hydrogen or methyl; R.sub.53 is hydrogen, methyl, OH or
OR.sub.54; and T.sub.10 is the divalent acyl residue of an
aliphatic or cycloaliphatic dicarboxylic acid of 13 to 60 carbon
atoms; and which contains at least one moiety of formula (101) and
at least one moiety T.sub.10.
2. A composition according to claim 1 comprising a) a polymeric
material containing a photochromic dye and c) a stabilizer
combination of i) a hydroxyphenyl triazine UV absorber and ii) at
least one further light stabilizer selected from the sterically
hindered amines.
3. Composition according to claim 1, which is an optical device, an
architectural or vehicle glazing, a greenhouse film, a coating, or
a construction element, in particular an ophthalmic lense.
4. Composition according to claim 1, wherein component (a) is
selectected from polyolefines, polycarbonate, polyesters, styrene
polymers or copolymers, polyacrylates, cellulose esters,
polyvinylalcohol, polyurethanes; in particular from polyethylene,
polypropylene, polyethylene terephthalate, polystyrene, high impact
polystyrene, polyvinylbutyrate, styrene-methacrylate,
styrene-acrylonitrile, glycole modified polyethyleneterephtalate,
polycarbonate, polymethylmethacrylate, polyvinylbutyral,
ethylene-vinyl acetate copolymer, ethylene-butyl acrylate
copolymer, and blends thereof.
5. Composition according to claim 1 containing a photochromic dye
selected from the naphthopyranes, benzopyranes, spiropyranes or
spirooxazines as component (b) in an amount of 0.001 to 10% by
weight, with respect to the total weight of the polymeric material
(a).
6. Composition of claim 2 wherein the sterically hindered amine
(ii) is a compound comprising at least one radical of the formula
IX, X and/or XI ##STR79## in which G is hydrogen or methyl, and
G.sub.1 and G.sub.2 are hydrogen, methyl or together are oxygen,
and having a molecular weight of 400 g/mol or higher.
7. Composition of claim 1 which is a 2- or multilayer system
wherein the UV absorber (i) is enriched in an upper layer
containing no photochromic dye, while a lower layer contains the
dye (b) and optionally the sterically hindered amine (ii).
8. Composition of claim 1 wherein the polymeric material (a)
contains 0.001 to 10% by weight of the stabilizer component (c)
comprising a ratio of UVA component (i) to sterically hindered
amine component (ii) in the range 0.01 to 100 parts (i) per 1 part
(ii).
9. Composition of claim 1 comprising as component (d) at least one
further additive selected from antioxidants, phosphites and
phosphonites, processing stabilizers, fillers, pigments, dyes,
clarifiers, modifiers, acid scavengers, flame retardants, further
light stabilizers.
10. Process of stabilizing a photochromic system containing a
photochromic dye in a polymer matrix against colour fading induced
by irradiation, which process comprises incorporation of a
hydroxyphenyl triazine UV absorber (i) and optionally a sterically
hindered amine light stabilizer into the polymer matrix and/or into
a polymer layer covering said polymer matrix, wherein the
hydroxyphenyl triazine UV absorber (i) is of formula I, II, III,
IV, V or (100) ##STR80## wherein Y is phenyl, naphthyl, or said
phenyl or said naphthyl substituted by one to three alkyl of 1 to 6
carbon atoms, by halogen, by hydroxy or by alkoxy of 1 to 6 carbon
atoms or by mixtures thereof; or Y is Z.sub.1 or Z.sub.2; X is
Z.sub.1 or Z.sub.2; R.sub.1 is hydrogen, straight or branched chain
alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms,
phenylalkyl of 7 to 15 carbon atoms, halogen, --SR.sub.3,
--SOR.sub.3 or --SO.sub.2R.sub.3; or said alkyl, said cycloalkyl or
said phenylalkyl substituted by one to three halogen, --R.sub.4,
--OR.sub.5, --N(R.sub.5).sub.2, --COR.sub.5, --COOR.sub.5,
--OCOR.sub.5, --CN, --NO.sub.2, --SR.sub.5, --SOR.sub.5,
--SO.sub.2R.sub.5 or --P(O)(OR.sub.5).sub.2, morpholinyl,
piperidinyl, 2,2,6,6-tetramethylpiperidinyl, piperazinyl or
N-methylpiperidinyl groups or combinations thereof; or said alkyl
or said cycloalkyl interrupted by one to four phenylene, --O--,
--NR.sub.5--, --CONR.sub.5--, --COO--, --OCO-- or --CO groups or
combinations thereof; or said alkyl or said cycloalkyl both
substituted and interrupted by combinations of the groups mentioned
above; R.sub.3 is alkyl of 1 to 20 carbon atoms, alkenyl of 3 to 18
carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7
to 15 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl
substituted by one or two alkyl of 1 to 4 carbon atoms; R.sub.4 is
aryl of 6 to 10 carbon atoms or said aryl substituted by one to
three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8
carbon atoms or combinations thereof; cycloalkyl of 5 to 12 carbon
atoms; phenylalkyl of 7 to 15 carbon atoms or said phenylalkyl
substituted on the phenyl ring by one to three halogen, alkyl of 1
to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations
thereof; or straight or branched chain alkenyl of 2 to 18 carbon
atoms; R.sub.5 is defined as is R.sub.4; or R.sub.5 is also
hydrogen or straight or branched chain alkyl of 1 to 24 carbon
atoms, alkenyl of 2 to 24 carbon atoms; or R.sub.5 is a group for
formula ##STR81## T is hydrogen, oxyl, hydroxyl, --OT.sub.1, alkyl
of 1 to 24 carbon atoms, said alkyl substituted by one to three
hydroxy, benzyl or alkanoyl of 2 to 18 carbon atoms; T.sub.1 is
alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms,
alkenyl of 2 to 24 carbon atoms, cycloalkenyl of 5 to 12 carbon
atoms, phenylalkyl of 7 to 15 carbon atoms, a radical of a
saturated or unsaturated bicyclic or tricyclic hydrocarbon of 7 to
12 carbon atoms or aryl of 6 o 10 carbon atoms or said aryl
substituted by one to three alkyl of 1 to 4 carbon atoms; R.sub.2
is hydrogen, straight or branched chain alkyl of 1 to 24 carbon
atoms or cycloalkyl of 5 to 12 carbon atoms; or said alkyl or said
cycloalkyl substituted by one to four halogen, epoxy, glycidyloxy,
furyloxy, --R.sub.4, --OR.sub.5, --N(R.sub.5).sub.2,
--CON(R.sub.5).sub.2, --COR.sub.5, --COOR.sub.5, --OCOR.sub.5,
--OCOC(R.sub.5).dbd.C(R.sub.5).sub.2, --C(R.sub.5).dbd.CCOOR.sub.5,
--CN, --NCO, or ##STR82## or combinations thereof; or said alkyl or
said cycloalkyl interrupted by one to four epoxy, --O--,
--NR.sub.5--, --CONR.sub.5--, --COO--, --OCO--, --CO--,
--C(R.sub.5).dbd.C(R.sub.5)COO--, --OCOC(R.sub.5).dbd.C(R.sub.5)--,
--C(R.sub.5).dbd.C(R.sub.5)--, phenylene or phenylene-G-phenylene
in which G is --O--, --S--, --SO.sub.2--, --CH.sub.2-- or
--C(CH.sub.3).sub.2-- or combinations thereof, or said alkyl or
said cycloalkyl both substituted and interrupted by combinations of
the groups mentioned above; or R.sub.2 is --SO.sub.2R.sub.3 or
--COR.sub.6; R.sub.6 is straight or branched chain alkyl of 1 to 18
carbon atoms, straight or branched chain alkenyl of 2 to 12 carbon
atoms, phenoxy, alkylamino of 1 to 12 carbon atoms, arylamino of 6
to 12 carbon atoms, --R.sub.7COOH or --NH--R.sub.8--NCO; R.sub.7 is
alkylene of 2 to 14 carbon atoms or phenylene; R.sub.8 is alkylene
of 2 to 24 carbon atoms, phenylene, tolylene, diphenylmethane or a
group ##STR83## R.sub.1 and R.sub.1' are the same or different and
are as defined for R.sub.1; R.sub.2 and R.sub.2' are the same or
different and are as defined for R.sub.2; X and X' are the same or
different and are as defined for X; Y and Y' are the same or
different and are as defined for Y; t is 0 to 9; L is straight or
branched alkylene of 1 to 12 carbon atoms, cycloalkylene of 5 to 12
carbon atoms or alkylene substituted or interrupted by
cyclohexylene or phenylene; or L is benzylidene; or L is --S--,
--S--S--, --S--E--S--, --SO--, --SO.sub.2--, --SO--E--SO--,
--SO.sub.2--E--SO.sub.2--, --CH.sub.2--NH--E--NH--CH.sub.2-- or
##STR84## E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5
to 12 carbon atoms or alkylene interrupted or terminated by
cycloalkylene of 5 to 12 carbon atoms; n is 2, 3 or 4; when n is 2;
Q is straight or branched alkylene of 2 to 16 carbon atoms; or said
alkylene substituted by one to three hydroxy groups; or said
alkylene interrupted by one to three --CH.dbd.CH-- or --O--; or
said alkylene both substituted and interrupted by combinations of
the groups mentioned above; or Q is xylylene or a group
--CONH--R.sub.8--NHCO--,
--CH.sub.2CH(OH)CH.sub.2O--R.sub.9--OCH.sub.2CH(OH)CH.sub.2--,
--CO--R.sub.10--CO--, or
--(CH.sub.2).sub.m--COO--R.sub.11--OOC--(CH.sub.2).sub.m--, where m
is 1 to 3; or Q is ##STR85## R.sub.9 is alkylene of 2 to 50 carbon
atoms; or said alkylene interrupted by one to ten --O--, phenylene
or a group -phenylene-G-phenylene in which G is --O--, --S--,
--SO.sub.2--, --CH.sub.2-- or --C(CH.sub.3).sub.2--; R.sub.10 is
alkylene of 2 to 10 carbon atoms; or said alkylene interrupted by
one to four --O--, --S-- or --CH.dbd.CH--; or R.sub.10 is arylene
of 6 to 12 carbon atoms; R.sub.11 is alkylene of 2 to 20 carbon
atoms; or said alkylene interrupted by one to eight --O--; when n
is 3, Q is a group --[(CH.sub.2).sub.mCOO].sub.3--R.sub.12 where m
is 1 to 3, and R.sub.12 is an alkanetriyl of 3 to 12 carbon atoms;
when n is 4, Q is a group --[(CH.sub.2).sub.mCOO].sub.4--R.sub.13
where m is 1 to 3, and R.sub.14 is an alkanetetrayl of 4 to 12
carbon atoms; Z.sub.1 is a group of formula ##STR86## Z.sub.2 is a
group of formula ##STR87## where r.sub.1 and r.sub.2 are 1;
R.sub.14, R.sub.15, R.sub.16, R.sub.17, R.sub.18 , R.sub.19,
R.sub.20, R.sub.21, R.sub.22 and R.sub.23 are independently of one
another hydrogen, hydroxy, cyano, alkyl of 1 to 20 carbon atoms,
alkoxy of 1 to 20 carbon atoms, phenylalkyl of 7 to 15 carbon
atoms, cycloalkyl of 5 to 12 carbon atoms, cycloalkoxy of 5 to 12
carbon atoms, halogen, haloalkyl of 1 to 5 carbon atoms, sulfo,
carboxy, acylamino of 2 to 12 carbon atoms, acyloxy of 2 to 12
carbon atoms, alkoxycarbonyl of 2 to 12 carbon atoms or
aminocarbonyl; or R.sub.17 and R.sub.18 or R.sub.22 and R.sub.23
together with the phenyl radical to which they are attached are a
cyclic radical interrupted by one to three --O-- or --NR.sub.5--;
x.sub.2 is a number from 1 to 50; A.sub.1 is a group of the formula
(101) ##STR88## or has one of the meanings given for T.sub.10;
D.sub.1 is C.sub.4-C.sub.12 alkylene or said alkylene substituted
by OH or interrupted by O or both substituted by OH and interrupted
by O; L.sub.1 is C.sub.1-C.sub.18alkylene;
C.sub.5-C.sub.12cycloalkylene: C.sub.3-C.sub.18alkenylene; or one
of said residues substituted by phenyl,
C.sub.7-C.sub.11alkylphenyl, C.sub.5-C.sub.12cycloalkyl, OH,
halogen, C.sub.1-C.sub.18alkoxy, C.sub.5-C.sub.12cycloalkoxy,
C.sub.3-C.sub.18alkenyloxy, COOH; the R.sub.50 are independently of
each other H, OR.sub.54 or OH, with the proviso that at least one
of R.sub.50 or R.sub.53 is OH; the R.sub.54 are independently of
each other hydrogen, C.sub.1-C.sub.12alkyl or a radical of formula
--L.sub.1--CO--O--R.sub.55; R.sub.55 is H, C.sub.1-C.sub.18alkyl,
C.sub.2-C.sub.12hydroxyalkyl; R.sub.51 is hydrogen,
C.sub.1-C.sub.4alkyl, Cl, phenyl or a group --OR.sub.54; R.sub.52
is hydrogen or methyl; R.sub.53 is hydrogen, methyl, OH or
OR.sub.54; and T.sub.10 is the divalent acyl residue of an
aliphatic or cycloaliphatic dicarboxylic acid of 13 to 60 carbon
atoms; and which contains at least one moiety of formula (101) and
at least one moiety T.sub.10.
11. (canceled)
Description
[0001] The present invention relates to light stabilized polymer
compositions comprising a photochromic dye, to a process of
improving the stability and/or colour fastness of a photochromic
dye, and to the use of a certain stabilizer for improving the light
fastness of photochromic dyes or compositions containing them.
[0002] Photochromic systems comprise molecules able to change the
color due to a reversible transformation of a chemical species
induced by daylight.
[0003] Typical photochromic systems employ naphtho- or benzopyrans
(chromenes), spiropyrans, spirooxazines. These molecules have found
several fields of application especially in plastics (e.g.
ophthalmic lenses). One of the most severe limitations to a large
scale employment of such devices is due to the intrinsically poor
long term stability, e.g. the photostability of both colorless and
colored forms under conditions of more or less continuous
irradiation with daylight. WO 96/37576 notes some stabilization of
these systems using certain light stabilizers.
[0004] U.S. Pat. No. 5,770,115 pertains to compositions of a
carrier photochromic naphthopyran material and a stabilizer system
comprising a polyphenolic antioxidant, a ultraviolet light absorber
and a hindered amine light stabilizer. The stabilizer system is
used to improve the fatigue resistance of the photochromic
naphthopyran compounds.
[0005] It has now been found that an improved light stabilization
and color fastness of photochromic systems and the dyes used, e.g.
of marks and colorations on polymeric materials such as plastics
and elastomers, may be achieved using a specific UV absorber and
optional further stabilizer.
[0006] The UV absorbers are selected from the family of
hydroxyphenyltriazines; thus, present invention pertains to a
composition comprising [0007] a) a polymeric material containing
[0008] b) a photochromic dye and [0009] c) a stabilizer comprising
a hydroxyphenyl triazine UV absorber (i) conforming to formula I,
II, III, IV or V ##STR1## wherein
[0010] Y is phenyl, naphthyl, or said phenyl or said naphthyl
substituted by one to three alkyl of 1 to 6 carbon atoms, by
halogen, by hydroxy or by alkoxy of 1 to 6 carbon atoms or by
mixtures thereof; or Y is Z, or Z.sub.2; X is Z.sub.1 or
Z.sub.2;
[0011] R.sub.1 is hydrogen, straight or branched chain alkyl of 1
to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl
of 7 to 15 carbon atoms, halogen, --SR.sub.3, --SOR.sub.3 or
--SO.sub.2R.sub.3; or said alkyl, said cycloalkyl or said
phenylalkyl substituted by one to three halogen, --R.sub.4,
--OR.sub.5, --N(R.sub.5).sub.2, --COR.sub.5, --COOR.sub.5,
--OCOR.sub.5, --CN, --NO.sub.2, --SR.sub.5, --SOR.sub.5,
--SO.sub.2R.sub.5 or --P(O)(OR.sub.5).sub.2, morpholinyl,
piperidinyl, 2,2,6,6-tetramethylpiperidinyl, piperazinyl or
N-methylpiperidinyl groups or combinations thereof; or said alkyl
or said cycloalkyl interrupted by one to four phenylene, --O--,
--NR.sub.5--, --CONR.sub.5--, --COO--, --OCO-- or --CO groups or
combinations thereof; or said alkyl or said cycloalkyl both
substituted and interrupted by combinations of the groups mentioned
above;
[0012] R.sub.3 is alkyl of 1 to 20 carbon atoms, alkenyl of 3 to 18
carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7
to 15 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl
substituted by one or two alkyl of 1 to 4 carbon atoms;
[0013] R.sub.4 is aryl of 6 to 10 carbon atoms or said aryl
substituted by one to three halogen, alkyl of 1 to 8 carbon atoms,
alkoxy of 1 to 8 carbon atoms or combinations thereof; cycloalkyl
of 5 to 12 carbon atoms; phenylalkyl of 7 to 15 carbon atoms or
said phenylalkyl substituted on the phenyl ring by one to three
halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon
atoms or combinations thereof; or straight or branched chain
alkenyl of 2 to 18 carbon atoms;
[0014] R.sub.5 is defined as is R.sub.4; or R.sub.5 is also
hydrogen or straight or branched chain alkyl of 1 to 24 carbon
atoms, alkenyl of 2 to 24 carbon atoms; or R.sub.5 a group for
formula ##STR2##
[0015] T is hydrogen, oxyl, hydroxyl, --OT.sub.1 , alkyl of 1 to 24
carbon atoms, said alkyl substituted by one to three hydroxy;
benzyl or alkanoyl of 2 to 18 carbon atoms;
[0016] T.sub.1 is alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to
12 carbon atoms, alkenyl of 2 to 24 carbon atoms, cycloalkenyl of 5
to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, a radical
of a saturated or unsaturated bicyclic or tricyclic hydrocarbon of
7 to 12 carbon atoms or aryl of 6 to 10 carbon atoms or said aryl
substituted by one to three alkyl of 1 to 4 carbon atoms;
[0017] R.sub.2 is hydrogen, straight or branched chain alkyl of 1
to 24 carbon atoms or cycloalkyl of 5 to 12 carbon atoms; or said
alkyl or said cycloalkyl substituted by one to four halogen, epoxy,
glycidyloxy, furyloxy, --R.sub.4, --OR.sub.5, --N(R.sub.5).sub.2,
--CON(R.sub.5).sub.2, --COR.sub.5, --COOR.sub.5, --OCOR.sub.5,
--OCOC(R.sub.5).dbd.C(R.sub.5).sub.2, --C(R.sub.5).dbd.CCOOR.sub.5,
--CN, --NCO, or ##STR3## or combinations thereof; or said alkyl or
said cycloalkyl interrupted by one to four epoxy, --O--,
--NR.sub.5--, --CONR.sub.5--, --COO--, --OCO--, --CO--,
--C(R.sub.5).dbd.C(R.sub.5)COO--, --OCOC(R.sub.5).dbd.C(R.sub.5)--,
--C(R.sub.5).dbd.C(R.sub.5)--, phenylene or phenylene-G-phenylene
in which G is --O--, --S--, --SO.sub.2--, --CH.sub.2-- or
--C(CH.sub.3).sub.2-- or combinations thereof, or said alkyl or
said cycloalkyl both substituted and interrupted by combinations of
the groups mentioned above; or R.sub.2 is --SO.sub.2R.sub.3 or
--COR.sub.6;
[0018] R.sub.6 is straight or branched chain alkyl of 1 to 18
carbon atoms, straight or branched chain alkenyl of 2 to 12 carbon
atoms, phenoxy, alkylamino of 1 to 12 carbon atoms, arylamino of 6
to 12 carbon atoms, --R.sub.7COOH or --NH--R.sub.8--NCO;
[0019] R.sub.7 is alkylene of 2 to 14 carbon atoms or
phenylene;
[0020] R.sub.8 is alkylene of 2 to 24 carbon atoms, phenylene,
tolylene, diphenylmethane or a group ##STR4##
[0021] R.sub.1 and R.sub.1' are the same or different and are as
defined for R.sub.1;
[0022] R.sub.2 and R.sub.2' are the same or different and are as
defined for R.sub.2;
[0023] X, X' are the same or different and are as defined for X; Y
and Y' are the same or different and are as defined for Y; t is 0
to 9;
[0024] L is straight or branched alkylene of 1 to 12 carbon atoms,
cycloalkylene of 5 to 12 carbon atoms or alkylene substituted or
interrupted by cyclohexylene or phenylene; or L is benzylidene; or
L is --S--, --S--S--, --S--E--S--, --SO--, --SO.sub.2--,
--SO--E--SO--, --SO.sub.2--E--SO.sub.2,
--CH.sub.2--NH--E--NH--CH.sub.2-- or ##STR5##
[0025] E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5 to
12 carbon atoms or alkylene interrupted or terminated by
cycloalkylene of 5 to 12 carbon atoms; n is 2, 3 or 4;
[0026] when n is 2; Q is straight or branched alkylene of 2 to 16
carbon atoms; or said alkylene substituted by one to three hydroxy
groups; or said alkylene interrupted by one to three --CH.dbd.CH--
or --O--; or said alkylene both substituted and interrupted by
combinations of the groups mentioned above; or Q is xylylene or a
group --CONH--R.sub.8--NHCO--,
--CH.sub.2CH(OH)CH.sub.2O--R.sub.9--OCH.sub.2CH(OH)CH.sub.2--,
--CO--R.sub.10--CO--, or
--(CH.sub.2).sub.m--COO--R.sub.11--OOC--(CH.sub.2).sub.m--, where m
is 1 to 3; or Q is ##STR6##
[0027] R.sub.9 is alkylene of 2 to 50 carbon atoms; or said
alkylene interrupted by one to ten --O--, phenylene or a group
-phenylene-G-phenylene in which G is --O--, --S--, --SO.sub.2--,
--CH.sub.2-- or --C(CH.sub.3).sub.2--;
[0028] R.sub.10 is alkylene of 2 to 10 carbon atoms, or said
alkylene interrupted by one to four --O--, --S-- or --CH.dbd.CH--;
or R.sub.10 is arylene of 6 to 12 carbon atoms;
[0029] R.sub.11 is alkylene of 2 to 20 carbon atoms or said
alkylene interrupted by one to eight --O--;
[0030] when n is 3, Q is a group
--[(CH.sub.2).sub.mCOO].sub.3--R.sub.12 where m is 1 to 3, and
R.sub.12 is an alkanetriyl of 3 to 12 carbon atoms;
[0031] when n is 4, Q is a group
--[(CH.sub.2).sub.mCOO].sub.4--R.sub.13 where m is 1 to 3, and
R.sub.14 is an alkanetetrayl of 4 to 12 carbon atoms;
[0032] Z.sub.1 is a group of formula ##STR7##
[0033] Z.sub.2 is a group of formula ##STR8## where
[0034] r.sub.1 and r.sub.2 are 1;
[0035] R.sub.14, R.sub.15, R.sub.16, R.sub.17, R.sub.18, R.sub.19,
R.sub.20, R.sub.21, R.sub.22 and R.sub.23 are independently of one
another hydrogen, hydroxy, cyano, alkyl of 1 to 20 carbon atoms,
alkoxy of 1 to 20 carbon atoms, phenylalkyl of 7 to 15 carbon
atoms, cycloalkyl of 5 to 12 carbon atoms, cycloalkoxy of 5 to 12
carbon atoms, halogen, haloalkyl of 1 to 5 carbon atoms, sulfo,
carboxy, acylamino of 2 to 12 carbon atoms, acyloxy of 2 to 12
carbon atoms, alkoxycarbonyl of 2 to 12 carbon atoms or
aminocarbonyl; or R.sub.17 and R.sub.18 or R.sub.22 and R.sub.23
together with the phenyl radical to which they are attached are a
cyclic radical interrupted by one to three --O-- or
--NR.sub.5--.
[0036] In another embodiment of the instant invention, the
s-triazine UV absorbers are those of formula I where X and Y are
Z.sub.1 or Z.sub.2;
[0037] R.sub.1 is hydrogen, straight or branched chain alkyl of 1
to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl
of 7 to 15 carbon atoms or halogen;
[0038] R.sub.2 is hydrogen, straight or branched chain alkyl of 1
to 24 carbon atoms or cycloalkyl of 5 to 12 carbon atoms; or said
alkyl or said cycloalkyl substituted by one to three --R.sub.4,
--OR.sub.5, --COOR.sub.5, --OCOR.sub.5 or combinations thereof; or
said alkyl or cycloalkyl interrupted by one to three epoxy, --O--,
--COO--, --OCO-- or --CO--;
[0039] R.sub.4 is aryl of 6 to 10 carbon atoms or said aryl
substituted by one to three halogen, alkyl of 1 to 8 carbon atoms,
alkoxy of 1 to 8 carbon atoms or combinations thereof; cycloalkyl
of 5 to 12 carbon atoms; phenylalkyl of 7 to 15 carbon atoms or
said phenylalkyl substituted on the phenyl ring by one to three
halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon
atoms or combinations thereof;
[0040] R.sub.5 is defined as is R.sub.4; or R.sub.5 is also
hydrogen or straight or branched chain alkyl of 1 to 24 carbon
atoms;
[0041] Z.sub.1 is a group of formula ##STR9##
[0042] Z.sub.2 is a group of formula ##STR10## where r.sub.1 and
r.sub.2 are each 1; and
[0043] R.sub.14, R.sub.15, R.sub.16, R.sub.17, R.sub.18, R.sub.19,
R.sub.20, R.sub.21, R.sub.22 and R.sub.23 are independently of one
another hydrogen, hydroxy, cyano, alkyl of 1 to 20 carbon atoms,
alkoxy of 1 to 20 carbon atoms, phenylalkyl of 7 to 15 carbon
atoms, cycloalkyl of 5 to 12 carbon atoms, cycloalkoxy of 5 to 12
carbon atoms, halogen, haloalkyl of 1 to 5 carbon atoms, sulfo,
carboxy, acylamino of 2 to 12 carbon atoms, acyloxy of 2 to 12
carbon atoms, or alkoxycarbonyl of 2 to 12 carbon atoms or
aminocarbonyl.
[0044] Preferred are, for example, those conforming to the general
structure ##STR11## wherein
[0045] R.sub.28 is (CH.sub.2--CH.sub.2--O--).sub.n--R.sub.29;
--CH.sub.2--CH(OH)--CH.sub.2--O--R.sub.29; or
--CH(R.sub.30)--CO--O--R.sub.40; n is 0 or 1; R.sub.29 is
C.sub.1-C.sub.13alkyl or C.sub.2-C.sub.20alkenyl or
C.sub.6-C.sub.12aryl or CO--C.sub.1-C.sub.18alkyl; R.sub.30 is H or
C.sub.1-C.sub.8alkyl; R.sub.40 is C.sub.1-C.sub.12alkyl or
C.sub.2-C.sub.12alkenyl or C.sub.5-C.sub.6cycloalkyl.
[0046] A further example of hydroxyphenyltriazines (i) is the
compound (a) [0047] a)
2-(2-hydroxy-4-[2-ethylhexyl]oxyphenyl)-4,6-di(4-phenylphenyl)-1,3,5-tria-
zine,
[0048] Compound UV1 as used in the examples below is identical with
the above compound a (also disclosed as compound A8 of
US-6060543).
[0049] Hydroxyphenyl triazine UV absorber are described e.g. in
GB-A-975966, EP-A-434608, U.S. Pat. No. 4,619,956, U.S. Pat. No.
5,298,067, EP-A-530135, EP-A-520938, EP-A-531258, U.S. Pat. No.
5,556,973, U.S. Pat. No. 5,959,008, U.S. Pat. No. 6,184,375, U.S.
Pat. No. 6,117,997; for example in U.S. Pat. No. 5,998,116, U.S.
Pat. No. 6,255,483, U.S. Pat. No. 6060543.
[0050] Of interest are also such compositions wherein the
hydroxyphenyl triazine UV absorber (i) is an oligo- or polyester of
formula (100) ##STR12## in which [0051] x.sub.2 is a number from 1
to 50; [0052] A.sub.1 is a group of the formula (101) ##STR13## or
has one of the meanings given for T.sub.10; [0053] D.sub.1 is
C.sub.4-C.sub.12 alkylene or said alkylene substituted by OH or
interrupted by 0 or both substituted by OH and interrupted by 0;
[0054] L.sub.1 is C.sub.1-C.sub.18alkylene;
C.sub.5-C.sub.12cycloalkylene; C.sub.3-C.sub.18alkenylene; or one
of said residues substituted by phenyl,
C.sub.7-C.sub.11alkylphenyl, C.sub.5-C.sub.12cycloalkyl, OH,
halogen, C.sub.1-C.sub.18alkoxy, C.sub.5-C.sub.12cycloalkoxy,
C.sub.3-C.sub.18alkenyloxy, COOH; [0055] the R.sub.50 are
independently of each other H, OR.sub.54 or OH, with the proviso
that at least one of R.sub.50 or R.sub.53 is OH; [0056] the R.sub.5
are independently of each other hydrogen, C.sub.1-C.sub.12alkyl or
a radical of formula --L.sub.1--CO--O--R.sub.55; [0057] R.sub.55 is
H, C.sub.1-C.sub.18alkyl, C.sub.2-C.sub.12hydroxyalkyl; [0058]
R.sub.5, is hydrogen, C.sub.1-C.sub.4alkyl, Cl, phenyl or a group
--OR.sub.54; [0059] R.sub.52 is hydrogen or methyl; [0060] R.sub.5
is hydrogen, methyl, OH or OR.sub.54; and [0061] T.sub.10 is the
divalent acyl residue of an aliphatic or cycloaliphatic
dicarboxylic acid of 13 to 60 carbon atoms; and which contains at
least one moiety of formula (101) and at least one moiety
T.sub.10.
[0062] In a preferred compound, Li is C.sub.1-C.sub.4alkylene,
especially C.sub.2-C.sub.4alkylidene or methylene. D.sub.1 is
advantageously C.sub.4-C.sub.12alkylene or C.sub.4-C.sub.10alkylene
interrupted by O.
[0063] T.sub.10 as the divalent acyl residue of an aliphatic or
cycloaliphatic dicarboxylic acid of 13 to 60 carbon atoms includes,
for example, aliphatic diacyls wherein the 2 carbonyl groups are
interconnected by C.sub.11-C.sub.58alkylene or -alkenylene or
alkylene interrupted by cycloalkylene or cycloalkenylene, each of
which is unsubstituted or substituted by alkyl, and containing 11
to 58 carbon atoms in total, preferably 20 to 50 carbon atoms.
Alkylene or alkenylene may be branched or unbranched, or,
preferably not adjacent to an ethylenic double bond, interrupted by
oxygen. In preferred compounds, T.sub.10 is --CO--T.sub.10'--CO--,
wherein T.sub.10' is C.sub.20-C.sub.50alkylene or
C.sub.20-C.sub.50alkylene interrupted by one or more oxygen atoms;
especially preferred is unbranched C.sub.20-C.sub.50alkylene. In
further preferred compounds, T.sub.10 is --CO--T.sub.10'--CO--,
wherein T.sub.10' is alkylene interrupted by
C.sub.5-C.sub.12cycloalkylene or C.sub.5-C.sub.12cycloalkenylene or
said cycloalkylene or cycloalkenylene substituted by alkyl and
containing 11 to 58 carbon atoms, especially 20-50 carbon atoms, in
total; especially preferred cycloalkylene is cyclohexylene;
especially preferred cycloalkenylene is cyclohexenylene. Valuable
spacer groups T.sub.10' are, for example, of the formula 102
##STR14## wherein R.sub.56 is --(C.sub.bH.sub.2b)-- and R.sub.57 is
--(C.sub.cH.sub.2c)-- and [0064] R.sub.58, R.sub.59 and R.sub.60
are --(C.sub.dH.sub.2d)--H, --(C.sub.eH.sub.2e)--H, and
--(C.sub.fH.sub.2f)--H, respectively, where b, is from the range
0-7, and each of the indices b-f is from the range 0-20, with the
condition that the sum b.sub.1+b+c+d+e+f is from the range 15-45,
or of the formula 103 ##STR15## wherein [0065] R.sub.61 and
R.sub.62 each are C.sub.1-C.sub.18alkylene and each of R.sub.63,
R.sub.64, R.sub.65 and R.sub.66, independently, are H or
C.sub.1-C.sub.18alkyl, and R.sub.65 and R.sub.66 together may also
be a chemical bond, with the condition that the total number of
carbon atoms in formula 103 ranges from 20 to 50.
[0066] Of special technical importance are spacer groups T.sub.10'
of the formula 103 wherein R.sub.61, and R.sub.62 independently are
alkylene of 4-12 carbon atoms, each of R.sub.63 and R.sub.64,
independently, are C.sub.4-C.sub.12alkyl, while R.sub.65 and
R.sub.66 are hydrogen.
[0067] In the compounds of present formula (100), most preferably,
the R.sub.50 are OH; [0068] the Ru are hydrogen or methyl; [0069]
R.sub.5, is hydrogen, methyl or a group --OR.sub.54; [0070]
R.sub.52 is hydrogen; [0071] R.sub.53 is hydrogen, OH or
methyl.
[0072] Terminal groups of the oligomer or polymer of formula (100)
usually are --O--D.sub.1--OR.sub.67, or --OR.sub.67 if bonded to
A.sub.1 (left side of formula 100), [0073] or --A.sub.1--OR.sub.67,
such as --T.sub.10'--COOR.sub.67 or --[formula 101]--OR.sub.67, or
--R.sub.67 if bonded to O (right side of formula 100), [0074] where
R.sub.67 is H or C.sub.1-C.sub.8alkyl.
[0075] For example, the ester of formula (100) may conform to the
formula (104) ##STR16## in which [0076] x.sub.2 is a number from 1
to 20; [0077] the number y is at least 1 and ranges from
(x.sub.2+z-1) to (x.sub.2+z+1); [0078] z is a number from 1 to 20;
and [0079] R.sub.68 is hydrogen, C.sub.1-C.sub.12alkyl;
C.sub.5-C.sub.12cycloalkyl; C.sub.2-C.sub.12alkenyl; phenyl;
C.sub.7-C.sub.11alkylphenyl; C.sub.1-C.sub.12alkyl substituted by
phenyl, OH, halogen; C.sub.1-C.sub.18alkoxy,
C.sub.5-C.sub.12cycloalkoxy, C.sub.3-C.sub.18alkenyloxy or COOH;
especially hydrogen or C.sub.1-C.sub.4alkyl; [0080] R.sub.67 is
hydrogen or C.sub.1-C.sub.8alkyl; [0081] R.sub.69 is hydrogen or
C.sub.1-C.sub.4alkyl; [0082] D.sub.1 is C.sub.4-C.sub.8alkylene or
C.sub.4-C.sub.10alkylene interrupted by O; and T.sub.10' is
C.sub.20-C.sub.50alkylene or C.sub.20-C.sub.50alkylene interrupted
by one or more oxygen atoms; and all other symbols are as defined
for formula 100 above.
[0083] T.sub.10' may also be alkylene interrupted by
C.sub.5-C.sub.12cycloalkylene or said cycloalkylene, especially
cyclohexylene, substituted by alkyl and containing 20-50 carbon
atoms in total.
[0084] In the oligo- or polyester of formula (104), each of the
divalent structural units identified by the indices x.sub.2 and z
bond to the structural unit --O--D.sub.1-- identified by the index
y, and/or to an end group R.sub.67 or OR.sub.67.
[0085] In compounds of the formula (100), x.sub.2 is preferably
from the range 2-50, more preferably from the range 2-20,
especially 4-12; the number of triazine moieties of the formula 101
to diacid residues T.sub.10 preferably ranges from about 1:3 to
about 10:1, more preferably from about 1:1 to about 5:1. In
compounds of the formula (104), each of x.sub.2 and z are
preferably from the range 1-16; more preferably, x.sub.2 is from
the range 1-10 and z is ranging from 2-12.
[0086] Oligomeric or polymeric esters of the invention such as
those of formula 100 or 104 usually have a molecular weight within
the range 1000 to 50000 g/mol, more preferably 1500 to 20000 g/mol,
most preferably 2000 to 10000 g/mol (number average Mn as
determined by gel permeation chromatography GPC).
[0087] Alkylphenyl is alkyl-substituted phenyl;
C.sub.7-C.sub.14alkylphenyl embraces examples such as methylphenyl
(tolyl), dimethylphenyl (xylyl), trimethylphenyl (mesityl),
ethylphenyl, propylphenyl, butylphenyl, dibutylphenyl,
pentylphenyl, hexylphenyl, heptylphenyl and octylphenyl.
[0088] Phenylalkyl is phenyl-substituted alkyl;
C.sub.7-C.sub.11phenylalkyl embraces examples such as benzyl,
.alpha.-methylbenzyl, .alpha.-ethylbenzyl,
.alpha.,.alpha.-dimethylbenzyl, phenylethyl, phenylpropyl,
phenylbutyl and phenylpentyl.
[0089] Alkyl interrupted by O can generally comprise one or more
nonadjacent oxygen atom(s). Preferably, a carbon atom of an
alkylene chain such as D.sub.1 or T.sub.10' bonds to not more than
1 heteroatom.
[0090] Within the scope of the stated definitions, the alkyl
radicals are branched or unbranched alkyl such as methyl, ethyl,
propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl,
2-ethylbutyl, n-pentyl, isopentyl, 1-methylpentyl,
1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl,
1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl,
2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl,
nonyl, decyl, undecyl, 1-methylundecyl, dodecyl,
1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl,
hexadecyl, heptadecyl and octadecyl.
[0091] Alkylene such as of L.sub.1 or D.sub.1 derives from such
alkyls by abstraction of an hydrogen atom.
[0092] Within the scope of the stated definitions, the alkenyl
radicals include allyl, isopropenyl, 2-butenyl, 3-butenyl,
isobutenyl, n-penta-2,4-dienyl, 3-methyl-but-2-enyl; n-oct-2-enyl,
n-dodec-2-enyl, isododecenyl, n-octadec-2-enyl and
n-octadec4-enyl.
[0093] The heavy chains of T.sub.10, e.g. alkylene groups of
T.sub.10', may have a certain molecular distribution around their
main component. Ranges may be, for example, from 22-26, 28-32 or
34-38 C-atoms. It is however also possible that broader ranges are
used such as for example from 20 to 40, from 30 to 50 or from 30 to
40 carbon atoms, each for T.sub.10' in total.
[0094] Since the educts for preparing a compound of formula (100)
or (104) are commercial products, they may vary within certain
specifications. This is particularly the case for high molecular
weight diacids from which the T.sub.10 groups are derived, when
T.sub.10 is C.sub.20-C.sub.60alkylene (which may be interrupted as
described above).
[0095] Commercially available diacids or diacid esters may also
contain small amounts of chains below C.sub.20. Therefore mixtures
of compounds wherein T.sub.10 is a mixture containing up to 10% of
diacyl chains below 20 carbon atoms and 90 to 100% of diacyl chains
between 20 and 60, particularly between 20 and 40 carbon atoms are
also subject of the invention. Percentage is weight percent, based
on the total mixture.
[0096] Present invention also pertains to an oligoester or
polyester which is obtained by reacting a tris-aryl-triazine of the
formula (105) ##STR17## and a compound of the formula
R.sub.67--O--T.sub.10--O--R.sub.67, where Y.sub.1 is CO and all
other all symbols are as defined above, with a diol
HO--D.sub.1--OH.
[0097] Hydroxyphenyl triazine UV absorber (i) of formula
(100)-(105) may be prepared as described in the international
patent application with application no. EP2004/050804.
[0098] Preference is given to hydroxyphenyl triazine UV absorber
(i) of the formula I, II, III, IV or V.
[0099] Preferred further light stabilizers to be employed are
sterically hindered amines (HALS), especially selected from
oligomeric and monodispersed HALS, oligomeric HALS of the
alkoxyamine class (NOR-HALS), and low basicity HALS like
piperazinones (such as products described in WO 00/31069),
morpholinones (see WO 99/14206), piperazinediones (see
DE-A-19924984), and thioimidazolidinones (see WO 01/62739).
[0100] Thus, present invention specifically pertains to a
composition comprising [0101] a) a polymeric material containing
[0102] b) a photochromic dye and [0103] c) a stabilizer combination
of [0104] i) a hydroxyphenyl triazine UV absorber and [0105] ii) at
least one further light stabilizer selected from the sterically
hindered amines (HALS).
[0106] The compositions of the invention are useful for all
applications wherein a photochromic effect is to be achieved. Some
examples are described below: [0107] Optical devices such as
particular types of ophthalmic lenses, referred to as
"photochromatic", where the beneficial neutralization of harmful UV
solar radiation and the anti-glare effect are effective only when
needed, allowing the use of the sunglasses with the photochromatic
lenses also indoor. Such lenses are often made of polyacrylates,
cellulose esters, polyvinylalcohol, polyurethanes, polycarbonates,
polyesters such as polyethyleneterephtalates, polyvinylbutyrate,
polystyrenes and related copolymers such as styrene-methacrylate or
styrene-acrylonitrile. The systems may further be applied in
optical films as seen in WO 97/32225, and U.S. Pat. Nos. 4,871,784
and 5,217,794 which are incorporated herein by reference. [0108]
Additional applications can be in the field of glazing, where
filtration of visible light triggered by the UV part of the solar
radiation may enhance the comfort inside a building or vehicle
and/or contribute to reduce costs for conditioning an indoor
environment. The photochromic system can be present either in the
plastic window or used in a film that is laminated onto or embedded
in a glass or plastic window. Typical materials used in these
contexts are polyethyleneterephtalate, glycole modified
polyethyleneterephtalate, polycarbonate, polymethylmethacrylate,
polyvinylbutyral, and/or as described in WO 92/01557, Japanese Nos.
75-33286; 93-143668; 95-3217 and 96-143831, and U.S. Pat. No.
5,643,676 which is incorporated herein by reference, for films and
glazings; or as seen in Japanese Nos. 8040018; 90-192118;
90-335037; 90-335038; 92-110128 and 94-127591, and U.S. Pat. No.
5,618,863 which is incorporated herein by reference, for
windscreens/vehicle glazings and intermediate layers. [0109] Also
greenhouse plastic covers can be additivated with photochromes,
aiming at reducing light intensity inside the greenhouse, that
eventually turns into heat, as excessive heat may be detrimental to
some crops and/or inhibit growth. Low density polyethylene, linear
low density polyethylene, ethylene-vinyl acetate copolymer (EVA)
and ethylene-butyl acrylate copolymer and blends of the mentioned
polymers are typical materials for plastic covers used in
agriculture. [0110] Photochromic coatings. [0111] Construction
elements or articles containing photochromic parts for the purpose
of labelling, signalling, decoration etc.
[0112] In general, the polymeric material of component a) may be
selected from polymers listed below: [0113] 1. Polymers of
monoolefins and diolefins, for example polypropylene,
polyisobutylene, polybut-1-ene, poly4-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).
[0114] 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: [0115] a) radical polymerisation (normally under high
pressure and at elevated temperature). [0116] 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). [0117] 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). [0118] 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 (EM), LLDPE/EVA, LLDPE/EAA and alternating or
random polyalkylene/carbon monoxide copolymers and mixtures thereof
with other polymers, for example polyamides. [0119] 4. Hydrocarbon
resins (for example C.sub.5-C.sub.9) including hydrogenated
modifications thereof (e.g. tackifiers) and mixtures of
polyalkylenes and starch.
[0120] 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. [0121] 5. Polystyrene,
poly(p-methylstyrene), poly(.alpha.-methylstyrene). [0122] 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. [0123] 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. [0124] 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). [0125] 6c. Hydrogenated aromatic
polymers derived from hydrogenation of polymers mentioned under
6a.).
[0126] Homopolymers and copolymers may have any stereostructure
including syndiotactic, isotactic, hemi-isotactic or atactic; where
atactic polymers are preferred. Stereoblock polymers are also
included. [0127] 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. [0128] 8. Halogen-containing polymers such as
polychloroprene, chlorinated rubbers, chlorinated and brominated
copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated
or sulfo-chlorinated 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. [0129] 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. [0130] 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. [0131] 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. [0132] 12. Homopolymers and copolymers of
cyclic ethers such as polyalkylene glycols, polyethylene oxide,
polypropylene oxide or copolymers thereof with bisglycidyl ethers.
[0133] 13. Polyacetals such as polyoxymethylene and those
polyoxymethylenes which contain ethylene oxide as a comonomer;
polyacetals modified with thermoplastic polyurethanes, acrylates or
MBS. [0134] 14. Polyphenylene oxides and sulfides, and mixtures of
polyphenylene oxides with styrene polymers or polyamides. [0135]
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. [0136] 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,-trimethylhexamethylene
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).
[0137] 17. Polyureas, polyimides, polyamide-imides, polyetherimids,
polyesterimids, polyhydantoins and polybenzimidazoles. [0138] 18.
Polyesters derived from dicarboxylic acids and diols and/or from
hydroxycarboxylic acids or the corresponding lactones, for example
polyethylene terephthalate (PET), 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. Specific
examples are PET, polybutylene terephthalate (PBT),
polyethylenenaphthalenate (PEN), polytrimethylene terephthalate
(PTT), and their copolyesters, for example with isophthalic acid,
di-ethylene glycol, 1,4-bis(hydroxymethyl)cyclohexane. [0139] 19.
Polycarbonates and polyester carbonates. [0140] 20. Polyketones.
[0141] 21. Polysulfones, polyether sulfones and polyether ketones.
[0142] 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. [0143] 23. Drying and non-drying
alkyd resins. [0144] 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.
[0145] 25. Crosslinkable acrylic resins derived from substituted
acrylates, for example epoxy acrylates, urethane acrylates or
polyester acrylates. [0146] 26. Alkyd resins, polyester resins and
acrylate resins crosslinked with melamine resins, urea resins,
isocyanates, isocyanurates, polyisocyanates or epoxy resins. [0147]
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. [0148] 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. [0149] 29. Blends of the aforementioned polymers
(polyblends), for example PP/EPDM, Polyamide/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.
[0150] Polymeric material useable for the present invention is
preferably synthetic organic polymeric material, for example,
material commonly used for electronic applications.
[0151] In particular the following polymers are preferred:
[0152] Polyolefines such as polyethylene and polypropylene,
polycarbonate, polyesters such as polyethylene terephthalate (PET)
and its copolyesters; styrene polymers or copolymers such as
polystyrene or high impact polystyrene (PS-HIPS); or the specific
polymers mentioned above.
[0153] The photochromic dye is usually selected from naphtho- and
benzopyranes (chromenes), or from spiropyranes or spirooxazines;
these components are commercial available.
[0154] Photochromic spiro-indolino-oxazine compounds useful in the
invention have the general structural formula (I'): ##STR18##
where: [0155] R.sub.1 and R.sub.2, either the same or different,
each represent independently a C.sub.1-C.sub.5alkyl group, linear
or branched; a phenyl group; or R.sub.1 and R.sub.2, together with
the carbon atom to which they are connected, jointly represent a
cycloalkyl(C.sub.4-C.sub.7)group,
bicycloalkyl(C.sub.6-C.sub.11)group, or
tricycloalkyl(C.sub.7-C.sub.13)group; [0156] R.sub.3 represents a
hydrogen atom; a C.sub.1-C.sub.5alkyl group, linear or branched; a
similar C.sub.1-C.sub.5alkyl group substituted with from 1 to 5
halogen atoms chosen from fluorine, chlorine, bromine or iodine,
hydroxy groups, C.sub.1-C.sub.5alkoxy groups,
C.sub.1-C.sub.5carboxy alkyl groups, cyano groups; a
C.sub.2-C.sub.5alkenyl group; a phenyl group; or benzyl group;
[0157] from R.sub.4 to R.sub.7, either the same or different, each
stand independently for a hydrogen atom; a C.sub.1-C.sub.5alkyl
group, linear or branched; a similar C.sub.1-C.sub.5alkyl group
substituted with from 1 to 5 halogen atoms chosen from fluorine,
chlorine, bromine or iodine, hydroxy groups, C.sub.1-C.sub.5alkoxy
groups, C.sub.1-C.sub.5carboxy alkyl groups, cyano groups; a
C.sub.2-C.sub.5alkenyl group; a phenyl group; a benzyl group; a
halogen atom chosen from either fluorine, chlorine, bromine or
iodine; a hydroxy group; a C.sub.1-C.sub.5alkoxy group; an amino
group; a monoalkyl(C.sub.1-C.sub.5)amino group; a
dialkyl(C.sub.1-C.sub.5)amino group; a
cyclo-alkyl(C.sub.3-C.sub.10)amino group; a piperidine, piperazine
or morpholine group; a carboxyl group; a carboxy
alkyl(C.sub.1-C.sub.5)group; a carboxy
alkenyl(C.sub.2-C.sub.5)group; a carboxamide group; a substituted
carboxamide N-alkyl(C.sub.1-C.sub.5)group; a substituted
carboxamide N,N-di-alkyl(C.sub.1-C.sub.5)group; a cyano group; a
nitro group; a sulfonic group; a (C.sub.1-C.sub.5)alkyl sulfonic
group; an aryl sulfonic group chosen from benzene sulfonic,
p-toluene sulfonic, p-chlorotoluene sulfonic groups; an aryl group
chosen from phenyl, biphenyl, naphthyl groups; [0158] R.sub.8
represents a hydrogen atom; a linear or branched
alkyl(C.sub.1-C.sub.5)group; a phenyl group; a halogen atom chosen
from either fluorine, chlorine, bromine; an
alkoxy(C.sub.1-C.sub.5)group; or a phenoxy group; [0159] A
represents an arenic, monocyclic or polycyclic group, chosen from
those that can be defined with formula (II'), (III'), (IV') or
(V'): ##STR19## two contiguous points from R.sub.9 to R.sub.12
represent the condensation position between the oxazinic nucleus in
the general formula (I') and the other two groups and
R.sub.13-R.sub.16 have the same meaning as R.sub.4-R.sub.7 in the
general formula (I'); or two contiguous groups together are
alkylene of 3-6 carbon atoms, or a corresponding azaalkylene or
oxaalkylene; or three contiguous groups jointly represent an
alkane-triyl, i.e. 3-valent saturated hydrocarbon residue, of 4-8
carbon atoms, or a corresponding aza- or oxa-alkane-triyl.
[0160] In the oxa- or aza-residues, one of the carbon atoms, along
with bonding hydrogens, if present, are replaced by oxygen,
nitrogen or NH.
[0161] Preferably in formula (I'): [0162] R.sub.1 and R.sub.2,
either the same or different, each represent independently a
methyl, ethyl, propyl or phenyl group, or together with the carbon
atom to which they are connected, jointly represent a cyclohexyl
group or a bi- or tricycloalkyl of 7-11 carbon atoms; [0163]
R.sub.3 represents a methyl, ethyl, propyl, phenyl, benzyl,
2-allyl, 2-hydroxyethyl or 2-carboxy-methyl group; [0164] from
R.sub.4 to R.sub.7, either the same or different, each stand
independently for the hydrogen atom, a fluorine, chlorine or
bromine atom, or a methyl, isopropyl, trifluoromethyl,
hydroxymethyl, benzyl, hydroxy, methoxy, amino, piperidino,
morpholino, carboxyl, carboxymethyl, N,N-di-methylcarboxamide,
cyano, nitro or phenyl group; [0165] R.sub.8 represents the
hydrogen atom, the chlorine atom, methyl, phenyl, or methoxy group;
and/or [0166] A is one of the groups with formula (II'), (III'),
(IV') or (V') where: [0167] two contiguous points from R.sub.9 to
R.sub.12 represent the condensation position between the oxazinic
nucleus in the general formula (I') and the other two groups in
addition to R.sub.13-R.sub.16 each represent independently the
hydrogen atom, a fluorine, chlorine or bromine atom, or a methyl,
ethyl, propyl, isopropyl, trifluoromethyl, hydroxymethyl, benzyl,
hydroxy, methoxy, amino, piperidino, morpholino, carboxyl,
carboxymethyl, N,N-dimethylcarboxamide, cyano, nitro or phenyl
group.
[0168] Specific examples of preferred spiro-indolino-oxazine
photochromic compounds useful in the present invention are:
1',3'-dihydro-5,7-dimethoxy-1'n-propyl-3'ethyl-3',4',5'-(and
3',5',6')-trimethyl-spiro[2H-1,4-benzoxazine-2,2'-[2H]indole]
(VI');
1,3-dihydro-1,3,3,4,5-(and
1,3,3,5,6)-pentamethylspiro[2H-indole-2,3'-[3H]pyrido[3,2-f][1,4]benzoxaz-
ine] (VII');
1,3-dihydro-1,3,3,4,5-(and
1,3,3,5,6)-pentamethylspiro[2H-indole-2,3'-[3H]naphth[2,1-b][1,4]oxazine]
(VIII'):
[0169] ##STR20##
[0170] Naphthopyran photochromic compounds usually have the general
structural formula (IX'): ##STR21## where: [0171] R.sub.1 to
R.sub.11, either the same or different, each stand independently
for a hydrogen atom; a C.sub.1-C.sub.5alkyl group, linear or
branched; a similar C.sub.1-C.sub.5alkyl group substituted with
from 1 to 5 halogen atoms chosen from fluorine, chlorine, bromine
or iodine, hydroxy groups, C.sub.1-C.sub.5alkoxy groups,
C.sub.1-C.sub.5carboxy alkyl groups, cyano groups; a
C.sub.2-C.sub.5alkenyl group; a phenyl group; a benzyl group; a
halogen atom chosen from either fluorine, chlorine, bromine or
iodine; a hydroxy group; a C.sub.1-C.sub.5alkoxy group; an amino
group; a monoalkyl(C.sub.1-C.sub.5)amino group; a
dialkyl(C.sub.1-C.sub.5)amino group; a
cyclo-alkyl(C.sub.3-C.sub.10)amino group; a piperidine, piperazine
or morpholine group; a carboxyl group; a carboxy
alkyl(C.sub.1-C.sub.5)group; a carboxy
alkenyl(C.sub.2-C.sub.5)group; a carboxamide group; a substituted
carboxamide N-alkyl(C.sub.1-C.sub.5)group; a substituted
carboxamide N,N-di-alkyl(C.sub.1-C.sub.5)group; a cyano group; a
nitro group; a sulfonic group; a (C.sub.1-C.sub.5)alkyl sulfonic
group; an aryl sulfonic group chosen from benzene sulfonic,
p-toluene sulfonic, p-chlorotoluene sulfonic groups; an aryl group
chosen from phenyl, biphenyl, naphthyl groups;
[0172] A represents an arenic polycyclic group, chosen from those
that can be defined with formula (X'): ##STR22## two contiguous
points from R.sub.12 to R.sub.15 represent the condensation
position between the pyran nucleus in the general formula (IX') and
the other two groups in addition to R.sub.16-R.sub.19 have the same
meaning as R.sub.1-R.sub.11 in the general formula (IX').
[0173] Preferably in formula (IX'): [0174] R.sub.1 to R.sub.11,
either the same or different, each stand independently for the
hydrogen atom, a fluorine, chlorine or bromine atom, or a methyl,
isopropyl, trifluoromethyl, hydroxymethyl, benzyl, hydroxy,
methoxy, amino, piperidino, morpholino, carboxyl, carboxymethyl,
N,N-dimethylcarboxamide, cyano, nitro or phenyl group; [0175] A is
one of the groups with formula (X') where: [0176] two contiguous
points from R.sub.12 to R.sub.15 represent the condensation
position between the pyran nucleus in the general formula (IX') and
the other two groups in addition to R.sub.16-R.sub.19 each
represent independently the hydrogen atom, a fluorine, chlorine or
bromine atom, or a methyl, ethyl, propyl, isopropyl,
trifluoromethyl, hydroxymethyl, benzyl, hydroxy, methoxy, amino,
piperidino, morpholino, carboxyl, carboxymethyl,
N,N-dimethylcarboxamide, cyano, nitro or phenyl group.
[0177] Specific examples of preferred naphtopyran photochromic
compounds useful in the present invention are: [0178]
3,3-diphenyl-3H-naphtho[2,1-b]pyran (XI'); [0179]
3-(2-fluorophenyl)-3-(3-methyl4-methoxyphenyl)-5-acetoxy-3H-naphtho[2,1-b-
]pyran (XII'): ##STR23## [0180]
3(2-fluorophenyl)-3-(4-methoxyphenyl)-3H-naphtho[2,1-b]pyran;
[0181]
3(2-fluorophenyl)-3(4'-methoxyphenyl)-8-methoxy-3H-naptho[2,1-b]pyran;
[0182]
3(2,4-dimethoxyphenyl)-3,4'-methoxyphenyl)-3H-naphto[2,1-b]pyran;
[0183]
3(2-fluorophenyl-3(3,4-dimethoxyphenyl)3H-naptho[2,1-b]pyran;
[0184]
3(2-methyl-4-methoxyphenyl)-3-(4-methoxyphenyl)-3H-naphto[2,1-b]p-
yran; [0185]
3-(2-methylphenyl)-3(4-methoxyphenyl)-3H-naphtho[2,1-b]pyran;
[0186] 3-phenyl-3(2,4-dimethoxyphenyl)-3H-naphtho[2,1-b]pyran; and
[0187]
3(2,6-difluorophenyl)-3(4-methoxyphenyl)-3H-naphtho[2,1-b]pyran.
[0188] Preferred naphthopyranes also include those of the formulae
##STR24## where each of R.sub.31, R.sub.32, R.sub.33, R.sub.34,
R.sub.35 independently may be hydrogen, a hydrocarbon of 1 to 18
carbon atoms such as phenyl, naphthyl, alkyl, optionally
substituted by OH, C.sub.1-C.sub.6alkoxy; --NR'R''; --NO.sub.2;
where R' and R'' independently are H or C.sub.1-C.sub.12alkyl,
C.sub.4-C.sub.12cycloalkyl, C.sub.7-C.sub.13phenylalkyl, or
together are tetramethylene or pentamethylene or O-interrupted
tetramethylene.
[0189] Benzopyranes, another class of chromenes, include those of
the formula ##STR25## where each of R.sub.41, R.sub.42, R.sub.43,
R.sub.44, R.sub.45 independently may be hydrogen, a hydrocarbon of
1 to 18 carbon atoms such as phenyl, naphthyl, alkyl, optionally
substituted by OH, C.sub.1-C.sub.6alkoxy; --NR'R''; --NO.sub.2;
where R' and R'' independently are H or C.sub.1-C.sub.12alkyl,
C.sub.4-C.sub.12cycloalkyl, C.sub.7-C.sub.13phenylalkyl, or
together are tetramethylene or pentamethylene or O-interrupted
tetramethylene.
[0190] For example, a chromene may be selected from naphthopyrans
of the formula ##STR26## wherein R is H; C.sub.1-C.sub.6alkyl;
C.sub.1-C.sub.6alkoxy; --NR'R''; --NO2; where R' and R''
independently are H or C.sub.1-C.sub.12alkyl,
C.sub.4-C.sub.12cycloalkyl, C.sub.7-C.sub.13phenylalkyl, or
together are tetramethylene or pentamethylene or O-interrupted
tetramethylene. Chromene1 as used in the examples below is of the
above formula where each R is H.
[0191] Preference is given to photochromic dyes (b) that do not
contain mercury.
[0192] Preferred sterically hindered amines (HALS) of component
(ii) are those comprising at least one radical of the formula IX, X
and/or XI ##STR27## in which [0193] G is hydrogen or methyl, and
[0194] G.sub.1 and G.sub.2 are hydrogen, methyl or together are
oxygen.
[0195] Of particular interest are systems comprising as component
(ii) at least one compound from the group of the sterically
hindered amines as described under the following classes (a') to
(I') which comprise at least one radical of the formula II or III:
(a') A compound of the formula (1a) ##STR28## in which n.sub.1 is a
number from 1 to 4, G and G.sub.1, independently of one another,
are hydrogen or methyl, [0196] G.sub.11 is hydrogen, O, hydroxyl,
NO, --CH.sub.2CN, C.sub.1-C.sub.18alkyl, C.sub.3-C.sub.8alkenyl,
C.sub.3-C.sub.8alkynyl, C.sub.7-C.sub.12aralkyl,
C.sub.1-C.sub.18alkoxy, C.sub.5-C.sub.12cycloalkoxy,
C.sub.7-C.sub.15phenylalkoxy, C.sub.1-C.sub.8alkanoyl,
C.sub.3-C.sub.5alkenoyl, C.sub.1-C.sub.18alkanoyloxy, benzyloxy,
glycidyl or a group --CH.sub.2CH(OH)--Z, where Z is hydrogen,
methyl or phenyl; or G.sub.11 is C.sub.1-C.sub.18alkoxy,
C.sub.5-C.sub.12cycloalkoxy or C.sub.7-C.sub.15phenylalkoxy each of
which is substituted in the aliphatic part by 1-3 OH groups;
G.sub.11 preferably being C.sub.1-C.sub.12alkoxy or cyclohexyloxy
or C.sub.2-C.sub.8hydroxyalkoxy or hydrogen or C.sub.1-C.sub.4alkyl
or allyl or benzyl or acetyl or acryloyl; especially H, methyl,
octyloxy, cyclohexyloxy or 2-hydroxy-2-methyl-propoxy, [0197] of
interest is also G.sub.11 being C.sub.1-C.sub.18alkoxy,
C.sub.5-C.sub.12cycloalkoxy, C.sub.7-C.sub.15phenylalkoxy,
benzyloxy or G.sub.11 being C.sub.1-C.sub.18alkoxy,
C.sub.5-C.sub.12cycloalkoxy or C.sub.7-C.sub.15phenylalkoxy each of
which is substituted in the aliphatic part by 1-3 OH groups; [0198]
and G.sub.12, if n.sub.1 is 1, is hydrogen, C.sub.1-C.sub.18alkyl
which is uninterrupted or interrupted by one or more oxygen atoms,
COO and/or CONH groups, or is cyanoethyl, benzoyl, glycidyl, a
monovalent radical of an aliphatic, cycloaliphatic, araliphatic,
unsaturated or aromatic carboxylic acid, carbamic acid or
phosphorus-containing acid or a monovalent silyl radical,
preferably a radical of an aliphatic carboxylic acid having 2 to 18
carbon atoms, of a cycloaliphatic carboxylic acid having 7 to 15
carbon atoms, or an .alpha.,.beta.-unsaturated carboxylic acid
having 3 to 5 carbon atoms or of an aromatic carboxylic acid having
7 to 15 carbon atoms, where each carboxylic acid can be substituted
in the aliphatic, cycloaliphatic or aromatic moiety by 1 to 3
--COOZ.sub.12 groups, in which Z.sub.12 is H,
C.sub.1-C.sub.20alkyl, C.sub.3-C.sub.12alkenyl,
C.sub.5-C.sub.7cycloalkyl, phenyl or benzyl, [0199] G.sub.12, if
n.sub.1 is 2, is C.sub.2-C.sub.12alkylene,
C.sub.4-C.sub.12alkenylene, xylylene, a divalent radical of an
aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic
acid, dicarbamic acid or phosphorus-containing acid or a divalent
silyl radical, preferably a radical of an aliphatic dicarboxylic
acid having 2 to 36 carbon atoms, or a cycloaliphatic or aromatic
dicarboxylic acid having 8-14 carbon atoms or of an aliphatic,
cycloaliphatic or aromatic dicarbamic acid having 8-14 carbon
atoms, where each dicarboxylic acid may be substituted in the
aliphatic, cycloaliphatic or aromatic moiety by one or two
--COOZ.sub.12 groups, [0200] G.sub.12, if n.sub.1 is 3, is a
trivalent radical of an aliphatic, cycloaliphatic or aromatic
tricarboxylic acid, which may be substituted in the aliphatic,
cycloaliphatic or aromatic moiety by --COOZ.sub.12, of an aromatic
tricarbamic acid or of a phosphorus-containing acid, or is a
trivalent silyl radical, preferred radicals including triacyl
radicals of nitrilo triacetic acid of benzene tricarboxylic acid,
[0201] and G.sub.12, if n.sub.1 is 4, is a tetravalent radical of
an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.
[0202] The carboxylic acid radicals mentioned above are in each
case taken to mean radicals of the formula (--CO).sub.xR, where x
is as defined above for n.sub.1, and the meaning of R arises from
the definition given above.
[0203] Alkyl with up to 20 carbon atoms is, for example, methyl,
ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl,
2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl,
n-tetradecyl, n-hexadecyl or n-octadecyl.
[0204] C.sub.1-C.sub.18alkoxy G.sub.11 is, for example, methoxy,
ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy,
isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy,
tetradecyloxy, hexadecyloxy and octadecyloxy.
C.sub.6-C.sub.12alkoxy, in particular heptoxy and octoxy, is
preferred.
[0205] C.sub.5-C.sub.12cycloalkoxy G.sub.11 is, for example,
cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy
and cyclododecyloxy. C.sub.5-C.sub.8cycloalkoxy, in particular
cyclopentoxy and cyclohexoxy, is preferred.
[0206] C.sub.7-C.sub.8phenylalkoxy is, for example, benzyloxy.
[0207] G.sub.11 as C.sub.1-C.sub.18alkoxy,
C.sub.5-C.sub.12cycloalkoxy or C.sub.7-C.sub.15phenylalkoxy
substituted in the aliphatic part by 1-3 OH groups is a radical
formed by abstraction of an carbon-bonded hydrogen atom preferably
from 2-methyl-2-propanol (tert.-butanol), 2-propanol,
2,2-dimethyl-1-propanol, 2-methyl-2-butanol, ethanol, 1-propanol,
1-butanol, 1-pentanol, 1-hexanol, 1-nonanol, 1-decanol,
1-dodecanol, 1-octadecanol, 2-butanol, 2-pentanol,
2-ethyl-1-hexanol, cyclohexanol, cyclooctanol, allyl alcohol,
phenethyl alcohol or 1-phenyl-1-ethanol; 1,2-ethanediol,
1,2-propanedial, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol,
1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol,
1,3-cyclohexanediol or 1,4-cyclohexanediol; glycerol,
1,1,1-tris(hydroxymethyl)methane,
2-ethyl-2-(hydroxymethyl-1,3-propanediol, 1,2,4-butanetriol or
1,2,6-hexanetriol. Most preferred hydroxy substituted G.sub.11 is
2-hydroxy-2-methylpropoxy.
[0208] Examples of several G.sub.12 radicals are given below.
[0209] If G.sub.12 is a monovalent radical of a carboxylic acid, it
is, for example, an acetyl, caproyl, stearoyl, acryloyl,
methacryloyl, benzoyl or
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl radical.
[0210] If G.sub.12 is a monovalent silyl radical, it is, for
example, a radical of the formula
--(C.sub.jH.sub.2j)--Si(Z').sub.2Z'', in which j is an integer in
the range from 2 to 5, and Z' and Z'', independently of one
another, are C.sub.1-C.sub.4alkyl or C.sub.1-C.sub.4alkoxy.
[0211] If G.sub.12 is a divalent radical of a dicarboxylic acid, it
is, for example, a malonyl, succinyl, glutaryl, adipoyl, suberoyl,
sebacoyl, maleoyl, itaconyl, phthaloyl, dibutylmalonyl,
dibenzylmalonyl, butyl(3,5-di-tert-butyl-4-hydroxybenzyl)malonyl or
bicycloheptenedicarbonyl radical or a group of the formula
##STR29##
[0212] If G.sub.12 is a trivalent radical of a tricarboxylic acid,
it is, for example, a trimellitoyl, citryl or nitrilotriacetyl
radical.
[0213] If G.sub.12 is a tetravalent radical of a tetracarboxylic
acid, it is, for example, the tetravalent radical of
butane-1,2,3,4-tetracarboxylic acid or of pyromellitic acid.
[0214] If G.sub.12 is a divalent radical of a dicarbamic acid, it
is, for example, hexamethylenedicarbamoyl or
2,4-toluylenedicarbamoyl radical.
[0215] Preference is given to compounds of the formula (1a) in
which G and G.sub.1 are hydrogen, G.sub.11 is hydrogen or methyl,
n.sub.1 is 2 and G.sub.12 is the diacyl radical of an aliphatic
dicarboxylic acid having 4-12 carbon atoms. (b') A compound of the
formula (1b) ##STR30## in which n.sub.2 is the number 1, 2 or 3,
and G, G.sub.1 and G.sub.11 are as defined under (a'), [0216]
G.sub.13 is hydrogen, C.sub.1-C.sub.12alkyl,
C.sub.2-C.sub.5hydroxyalkyl, C.sub.5-C.sub.7cycloalkyl,
C.sub.7-C.sub.8aralkyl, C.sub.1-C.sub.18alkanoyl,
C.sub.3-C.sub.5alkenoyl, benzoyl or a group of the formula
##STR31## and G.sub.14, if n.sub.2 is 1, is hydrogen,
C.sub.1-C.sub.18alkyl, C.sub.3-C.sub.8alkenyl,
C.sub.5-C.sub.7cycloalkyl, C.sub.1-C.sub.4alkyl which is
substituted by a hydroxyl, cyano, alkoxycarbonyl or carbamide group
or group of the formula --CONH--Z, or G.sub.14 is glycidyl, a group
of the formula --CH.sub.2--CH(OH)--Z or of the formula --CONH--Z,
in which Z is hydrogen, methyl or phenyl or CH.sub.2--OZ.sub.14
with Z.sub.14 being hydrogen or C.sub.1-C.sub.18alkyl; [0217]
G.sub.14, if n.sub.2 is 2, is C.sub.2-C.sub.12alkylene,
C.sub.6-C.sub.12arylene, xylylene, a --CH.sub.2--CH(OH)--CH.sub.2
group or a --CH.sub.2--CH(OH)--CH.sub.2--O--D--O-- group, in which
D is C.sub.2-C.sub.10alkylene, C.sub.6-C.sub.15arylene,
C.sub.6-C.sub.12cycloalkylene, or, provided that G.sub.13 is not
alkanoyl, alkenoyl or benzoyl, G.sub.14 can alternatively be
1-oxo-C.sub.2-C.sub.12alkylene, a divalent radical of an aliphatic,
cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or
alternatively the group --CO--, [0218] G.sub.14, if n.sub.2 is 3,
is a group ##STR32## or, if n.sub.2 is 1, G.sub.13 and G.sub.14
together can be the divalent radical of an aliphatic,
cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.
[0219] Some examples for the radicals G.sub.13, G.sub.14 and D are
given below.
[0220] Any alkyl substituents are as defined above for (a').
[0221] Any C.sub.5-C.sub.7cycloalkyl substituents are, in
particular, cyclohexyl.
[0222] C.sub.7-C.sub.8aralkyl G.sub.13 is, in particular,
phenylethyl or especially benzyl.
[0223] C.sub.2-C.sub.5hydroxyalkyl G.sub.13 is, in particular,
2-hydroxyethyl or 2-hydroxypropyl.
[0224] C.sub.1-C.sub.18alkanoyl G.sub.13 is, for example, formyl,
acetyl, propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl,
octadecanoyl, but preferably acetyl, and C.sub.3-C.sub.5alkenoyl
G.sub.13 is, in particular, acryloyl.
[0225] C.sub.2-C.sub.8alkenyl G.sub.14 is, for example, allyl,
methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.
[0226] G.sub.14 as a hydroxyl-, cyano-, alkoxycarbonyl- or
carbamide-substituted C.sub.1-C.sub.4alkyl can be, for example,
2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl,
methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl
or 2-(dimethylaminocarbonyl)ethyl.
[0227] Any C.sub.2-C.sub.12alkylene radicals are, for example,
ethylene, propylene, 2,2-dimethylpropylene, tetramethylene,
hexamethylene, octamethylene, decamethylene or dodecamethylene.
[0228] Any C.sub.6-C.sub.15arylene substituents are, for example,
o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
[0229] C.sub.6-C.sub.12cycloalkylene is, in particular,
cyclohexylene.
[0230] G.sub.14 as 1-oxo-C.sub.2-C.sub.12alkylene is preferably a
group ##STR33## (c') A compound of the formula (1c) ##STR34## in
which n.sub.3 is the number 1 or 2, G, G.sub.1 and G.sub.11 are as
defined under (a'), and G.sub.15 and G'.sub.15 if n.sub.3 is 1, are
independently C.sub.1-C.sub.12 alkyl, C.sub.2-C.sub.12alkenyl,
C.sub.7-C.sub.12aralkyl, or G.sub.15 is also hydrogen, or G.sub.15
and G'.sub.15 together are C.sub.2-C.sub.8alkylene,
C.sub.5-C.sub.15alkenylene, C.sub.2-C.sub.8hydroxyalkylene or
C.sub.4-C.sub.22acyloxyalkylene, and if n.sub.3 is 2, G.sub.15 and
G'.sub.15 together are the (--CH.sub.2).sub.2C(CH.sub.2--).sub.2
group.
[0231] C.sub.2-C.sub.8alkylene or C.sub.2-C.sub.8hydroxyalkylene
G.sub.15 and G'.sub.15 is, for example, ethylene, 1-methylethylene,
propylene, 2-ethylpropylene or
2-ethyl-2-hydroxymethylpropylene.
[0232] C.sub.4-C.sub.22acyloxyalkylene G.sub.15 and G'.sub.15 is,
for example, 2-ethyl-2-acetoxymethylpropylene. (d') A compound of
the formula (1d-1), (1d-2) or (1d-3), ##STR35## in which n.sub.4 is
the number 1 or 2, G, G.sub.1 and G.sub.11 are as defined under
(a'), [0233] G.sub.16 is hydrogen, C.sub.1-C.sub.12alkyl, allyl,
benzyl, glycidyl or C.sub.2-C.sub.6alkoxyalkyl, and [0234]
G.sub.17, if n.sub.4 is 1, is hydrogen, C.sub.1-C.sub.12alkyl,
C.sub.3-C.sub.5alkenyl, C.sub.7-C.sub.9aralkyl,
C.sub.5-C.sub.7cycloalkyl, C.sub.2-C.sub.4hydroxyalkyl,
C.sub.2-C.sub.6alkoxyalkyl, C.sub.6-C.sub.10aryl, glycidyl or a
group of the formula --(CH.sub.2).sub.p--COO--Q or
--(CH.sub.2).sub.p--O--CO--Q, in which p is 1 or 2, and Q is
C.sub.1-C.sub.4alkyl or phenyl, and [0235] G.sub.17, if n.sub.4 is
2, is C.sub.2-C.sub.12alkylene, C.sub.4-C.sub.12alkenylene,
C.sub.6-C.sub.12arylene, a group of the formula
--CH.sub.2--CH(OH)--CH.sub.2--O--D'--O--CH.sub.2--CH(OH)--CH.sub.2--,
in which D' is C.sub.2-C.sub.10alkylene, C.sub.6-C.sub.15arylene or
C.sub.6-C.sub.12cycloalkylene, or a group of the formula
--CH.sub.2CH(OD'')CH.sub.2--(OCH.sub.2--CH(OD'')CH.sub.2).sub.2--,
in which D'' is hydrogen, C.sub.1-C.sub.18alkyl, allyl, benzyl,
C.sub.2-C.sub.12alkanoyl or benzoyl, [0236] T.sub.1 and T.sub.2,
independently of one another, are hydrogen, C.sub.1-C.sub.18alkyl
or unsubstituted or halogen- or C.sub.1-C.sub.4alkyl-substituted
C.sub.6-C.sub.10aryl or C.sub.7-C.sub.9aralkyl, or [0237] T.sub.1
and T.sub.2 together with the carbon atom bonding them form a
C.sub.5-C.sub.14cycloalkane ring.
[0238] Any C.sub.1-C.sub.1.sub.2alkyl substituents are, for
example, methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl,
n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or
n-dodecyl.
[0239] Any C.sub.1-C.sub.18alkyl substituents can be, for example,
the abovementioned groups and in addition, for example, n-tridecyl,
n-tetradecyl, n-hexadecyl or n-octadecyl.
[0240] Any C.sub.2-C.sub.6alkoxyalkyl substituents are, for
example, methoxymethyl, ethoxymethyl, propoxymethyl,
tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl,
tert-butoxyethyl, isopropoxyethyl or propoxypropyl.
[0241] C.sub.3-C.sub.5alkenyl G.sub.17 is, for example, 1-propenyl,
allyl, methallyl, 2-butenyl or 2-pentenyl.
[0242] C.sub.7-C.sub.9aralkyl G.sub.17, T.sub.1 and T.sub.2 are, in
particular, phenethyl or especially benzyl. If T.sub.1 and T.sub.2
together with the carbon atom form a cycloalkane ring, this can be,
for example, a cyclopentane, cyclohexane, cyclooctane or
cyclododecane ring.
[0243] C.sub.2-C.sub.4hydroxyalkyl G.sub.17 is, for example,
2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or
4-hydroxybutyl.
[0244] C.sub.6-C.sub.10aryl G.sub.17, T.sub.1 and T.sub.2 are, in
particular, phenyl or .alpha.- or .beta.-naphthyl, which are
unsubstituted or substituted by halogen or
C.sub.1-C.sub.4alkyl.
[0245] C.sub.2-C.sub.12alkylene G.sub.17 is, for example, ethylene,
propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene,
octamethylene, decamethylene or dodecamethylene.
[0246] C.sub.4-C.sub.12alkenylene G.sub.17 is, in particular,
2-butenylene, 2-pentenylene or 3-hexenylene.
[0247] C.sub.6-C.sub.12arylene G.sub.17 is, for example, o-, m- or
p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
[0248] C.sub.2-C.sub.12alkanoyl D'' is, for example, propionyl,
butyryl, octanoyl, dodecanoyl, but preferably acetyl.
[0249] C.sub.2-C.sub.10alkylene, C.sub.6-C.sub.5arylene or
C.sub.6-C.sub.12cycloalkylene D' have, for example, one of the
definitions given for D under (b'). (e') A compound of the formula
(1e) ##STR36## in which n.sub.5 is the number 1 or 2, and G.sub.18
is a group of the formula ##STR37## in which G and G.sub.11 are as
defined under (a'), and G.sub.1 and G.sub.2 are hydrogen, methyl
or, together, are a substituent .dbd.O, [0250] E is --O-- or
--ND'''--, [0251] A is C.sub.2-C.sub.6alkylene or
--(CH.sub.2).sub.3--O-- and [0252] x.sub.1 is the number 0 or 1,
[0253] D''' is hydrogen, C.sub.1-C.sub.12alkyl,
C.sub.2-C.sub.12alkylene-N(D.sup.V).sub.2,
C.sub.2-C.sub.5hydroxyalkyl or C.sub.5-C.sub.7cycloalkyl, where
D.sup.V, independently, is hydrogen or butyl, [0254] G.sub.19 is
identical to G.sub.18 or is one of the groups
--N(G.sub.21)(G.sub.22), --OG.sub.23, --N(H)(CH.sub.2OG.sub.23) or
--N(CH.sub.2OG.sub.23).sub.2, [0255] G.sub.20, if n.sub.5=1, is
identical to G.sub.18 or G.sub.19 and, if n.sub.5=2, is an
--E--D.sup.IV--E-- group, in which D.sup.IV is
C.sub.2-C.sub.8alkylene or C.sub.2-C.sub.8alkylene which is
interrupted by 1 or 2 --NG.sub.21-- groups, [0256] G.sub.21 is
hydrogen, C.sub.1-C.sub.12alkyl, cyclohexyl, benzyl or
C.sub.1-C.sub.4-hydroxyalkyl or a group of the formula ##STR38##
[0257] G.sub.22 is C.sub.1-C.sub.12alkyl, cyclohexyl, benzyl or
C.sub.1-C.sub.4hydroxyalkyl, and [0258] G.sub.23 is hydrogen,
C.sub.1-C.sub.12alkyl or phenyl, or G.sub.21, and G.sub.22 together
are C.sub.4-C.sub.5alkylene or C.sub.4-C.sub.5oxaalkylene, for
example --CH.sub.2CH.sub.2--O--CH.sub.2CH.sub.2--, or a group of
the formula
--CH.sub.2CH.sub.2--N(G.sub.11)--CH.sub.2CH.sub.2--.
[0259] Some examples of the several variables in the formula (Ie)
are given below.
[0260] Any C.sub.1-C.sub.12alkyl substituents are, for example,
methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl,
n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or
n-dodecyl.
[0261] Any hydroxyalkyl substituents are, for example,
2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or
4-hydroxybutyl.
[0262] Any C.sub.5-C.sub.7cycloalkyl substituents are, for example,
cyclopentyl, cyclohexyl or cycloheptyl. Cyclohexyl is
preferred.
[0263] C.sub.2-C.sub.6alkylene A is, for example, ethylene,
propylene, 2,2-dimethylpropylene, tetramethylene or
hexamethylene.
[0264] If G.sub.21 and G.sub.22 together are
C.sub.4-C.sub.5alkylene or oxaalkylene, they are, for example,
tetramethylene, pentamethylene or 3-oxapentamethylene. (f') A
compound of the formula (1f) ##STR39## wherein G.sub.11 is as
defined under (a').
[0265] (g') Oligomeric or polymeric compounds whose recurring
structural unit contains a 2,2,6,6-tetraalkylpiperidinyl radical,
in particular polyesters, polyethers, polyamides, polyamines,
polyurethanes, polyureas, polyaminotriazines, poly(meth)acrylates,
poly(meth)acrylamides and copolymers thereof which contain such
radicals.
[0266] Examples of 2,2,6,6-polyalkylpiperidine compounds from this
class are the compounds of the following formulae. m.sub.1 to
m.sub.14 is a number from 2 to about 200, preferably 2 to 100, for
example 2to 50, 2to 40, 3to 40or 4to 10.
[0267] The meanings of the end groups which saturate the free
valences in the oligomeric or polymeric compounds listed below
depend on the processes used for the preparation of said compounds.
The end groups can also in addition be modified after the synthesis
of the compounds.
[0268] Examples for polymeric compounds are: [0269] 1) A compound
of the formula (1g) ##STR40## wherein G.sub.24, G.sub.25, G.sub.26,
G.sub.27 and G.sub.28, independently of one another, are a direct
bond or C.sub.1-C.sub.10alkylene, G.sub.11 is as defined under (a')
and m.sub.17 is a number from 1 to 50.
[0270] In the compound of the formula (1g), the end group bonded to
the >C.dbd.O group can be, for example, ##STR41## and the end
group bonded to the oxygen can be, for example ##STR42## [0271] 2)
Compound of the formula (2g) ##STR43## in which the index m.sub.18
ranges from 1 to 15; [0272] R.sub.12 is C.sub.2-C.sub.12alkylene,
C.sub.4-C.sub.12alkenylene, C.sub.5-C.sub.7cycloalkylene,
C.sub.5-C.sub.7cycloalkylene-di(C.sub.1-C.sub.4alkylene),
C.sub.1-C.sub.4alkylenedi(C.sub.5-C.sub.7cycloalkylene),
phenylenedi(C.sub.1-C.sub.4alkylene) or C.sub.4-C.sub.12alkylene
interrupted by 1,4-piperazinediyl, --O-- or >N--X.sub.1 with
X.sub.1 being C.sub.1-C.sub.12acyl or
(C.sub.1-C.sub.12alkoxy)carbonyl or having one of the definitions
of R.sub.14 given below except hydrogen; or R.sub.12 is a group of
the formula (2g') or (2g''); ##STR44## X.sub.2 being
C.sub.1-C.sub.18alkyl, C.sub.5-C.sub.12cycloalkyl which is
unsubstituted or substituted by 1, 2 or 3 C.sub.1-C.sub.4alkyl;
phenyl which is unsubstituted or substituted by 1, 2 or 3
C.sub.1-C.sub.4alkyl or C.sub.1-C.sub.4alkoxy;
C.sub.7-C.sub.9phenylalkyl which is unsubstituted or substituted on
the phenyl by 1, 2 or 3 C.sub.1-C.sub.4alkyl; and [0273] the
radicals X.sub.3 being independently of one another
C.sub.2-C.sub.12alkylene; the radicals A are independently of one
another --OR.sub.13, --N(R.sub.14)(R.sub.15) or a group of the
formula (2g'''); ##STR45## R.sub.13, R.sub.14 and R.sub.15, which
are identical or different, are hydrogen, C.sub.1-C.sub.18alkyl,
C.sub.5-C.sub.12cycloalkyl which is unsubstituted or substituted by
1, 2 or 3 C.sub.1-C.sub.4alkyl; C.sub.3-C.sub.18alkenyl, phenyl
which is unsubstituted or substituted by 1, 2 or 3
C.sub.1-C.sub.4alkyl or C.sub.1-C.sub.4alkoxy;
C.sub.7-C.sub.9phenylalkyl which is unsubstituted or substituted on
the phenyl by 1, 2 or 3 C.sub.1-C.sub.4alkyl; tetrahydrofurfuryl or
C.sub.2-C.sub.4alkyl which is substituted in the 2, 3 or 4 position
by --OH, C.sub.1-C.sub.8alkoxy, di(C.sub.1-C.sub.4alkyl)amino or a
group of the formula (2g.sup.IV); ##STR46## with Y being --O--,
--CH.sub.2--, --CH.sub.2CH.sub.2-- or >N--CH.sub.3, [0274] or
--N(R.sub.14)(R.sub.15) is additionally a group of the formula
(2g.sup.IV); [0275] X is --O-- or >N--R.sub.16; [0276] 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
1, 2 or 3 C.sub.1-C.sub.4alkyl; C.sub.7-C.sub.9phenylalkyl which is
unsubstituted or substituted on the phenyl by 1, 2 or 3
C.sub.1-C.sub.4alkyl; tetrahydrofurfuryl, a group of the formula
(2g.sup.V), ##STR47## or C.sub.2-C.sub.4alkyl which is substituted
in the 2, 3 or 4 position by --OH, C.sub.1-C.sub.8alkoxy,
di(C.sub.1-C.sub.4alkyl)amino or a group of the formula
(2g.sup.IV); [0277] R.sub.11 has one of the definitions given for
R.sub.16; and [0278] the radicals B have independently of one
another one of the definitions given for A. [0279] 3) A compound of
the formula (3g) ##STR48## in which G.sub.11 is as defined under
(a'), G.sub.29 and G.sub.32, independently of one another, are a
direct bond or a --N(X.sub.1)CO--X.sub.2--CO--N(X.sub.3)-- group,
where X.sub.1 and X.sub.3, independently of one another, are
hydrogen, C.sub.1-C.sub.8alkyl, C.sub.5-C.sub.12cycloalkyl, phenyl,
C.sub.7-C.sub.9phenylalkyl or a group of the formula ##STR49## and
X.sub.2 is a direct bond or C.sub.1-C.sub.4alkylene, G.sub.30,
G.sub.31, G.sub.34 and G.sub.35, independently of one another, are
hydrogen, C.sub.1-C.sub.30alkyl, C.sub.5-C.sub.12cycloalkyl or
phenyl, G.sub.33 is hydrogen, C.sub.1-C.sub.30alkyl,
C.sub.5-C.sub.12cycloalkyl, C.sub.7-C.sub.9phenylalkyl, phenyl or a
group of the formula (3g), and m.sub.19 is a number from 1 to
50.
[0280] In the compounds of the formula (3g), the end group bonded
to the 2,5-dioxopyrrolidine ring can be, for example, hydrogen, and
the end group bonded to the --C(G.sub.34)(G.sub.35)-- radical can
be, for example, ##STR50## [0281] 4) A product obtainable by
reacting an intermediate product, obtained by reaction of a
polyamine of the formula (4g) with cyanuric chloride, with a
compound of the formula (4g') ##STR51## in which m'.sub.20,
m''.sub.20 and m'''.sub.20, independently of one another, are a
number from 2 to 12, G.sub.36 is hydrogen, C.sub.1-C.sub.12alkyl,
C.sub.5-C.sub.12cycloalkyl, phenyl or C.sub.7-C.sub.9phenylalkyl,
and G.sub.11 is as defined under (a').
[0282] In general, the above reaction product can be represented
for example by a compound of the following 3 formulae. It can also
be in the form of a mixture of these three compounds: ##STR52##
[0283] 5) A compound of the formula (5g) ##STR53## in which
G.sub.11 is as defined under (a'), G.sub.37 is
C.sub.1-C.sub.10alkyl, C.sub.5-C.sub.12cycloalkyl,
C.sub.1-C.sub.4alkyl-substituted C.sub.5-C.sub.12cycloalkyl, phenyl
or C.sub.1-C.sub.10alkyl-substituted phenyl, G.sub.38 is
C.sub.3-C.sub.10alkylene and m.sub.21 is a number from 1 to 50.
[0284] In the compounds of the formula (5g), the terminal group
bonded to the silicon atom can be, for example,
(G.sub.37).sub.3Si--O--, and the terminal group bonded to the
oxygen can be, for example, --Si(G.sub.37).sub.3.
[0285] The compounds of the formula (5g) can also be in the form of
cyclic compounds if M.sub.21, is a number from 3 to 10, i.e. the
free valences shown in the structural formula then form a direct
bond. [0286] 6) A compound of the formula (6g) ##STR54## where E is
--O-- or --ND'''-- as defined under (e'), T.sub.3 is ethylene or
1,2-propylene, is the repeating structural unit derived from an
alpha-olefin copolymer with an alkyl acrylate or methacrylate;
preferably a copolymer of ethylene and ethyl acrylate, and where k
is 2 to 100. [0287] 7) A compound of the formula (7g) ##STR55##
[0288] wherein m is 1 to 100;
[0289] G.sub.50 is straight or branched chain alkylene of 1 to 18
carbon atoms, cycloalkylene of 5 to 8 carbon atoms, cycloalkenylene
of 5 to 8 carbon atoms, alkenylene of 3 to 18 carbon atoms, a
straight or branched chain alkylene of 1 to 4 carbon atoms
substituted by phenyl or by phenyl substituted by one or two alkyl
of 1 to 4 carbon atoms, with the proviso that in formula (7g)
successive hindered amine moieties can be oriented in either a head
to head or head to tail fashion;
[0290] T.sub.4 is hydrogen or ##STR56##
[0291] G.sub.55 is a straight or branched chain alkylene of 1 to 18
carbon atoms, cycloalkylene or cycloalkenylene of 5 to 8 carbon
atoms, phenylene or --NH-alkylene-NH-- of 2 to 18 carbon atoms
including 5-amino-1-aminomethyl-1,3,3-trimethylcyclohexane and
--NH-xylylene-NH--;
[0292] T.sub.5 is alkyl of 1 to 4 carbon atoms; ##STR57##
[0293] In the above shown oligomeric and polymeric compounds,
[0294] examples of alkyl are methyl, ethyl, propyl, isopropyl,
n-butyl, sec-butyl, isobutyl, tert-butyl, 2-ethylbutyl, n-pentyl,
isopentyl, 1-methylpentyl, 1,3-dimethylbutyl, n-hexyl,
1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl,
1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethyl-hexyl,
1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl,
undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl,
tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,
eicosyl and docosyl; [0295] examples of cycloalkyl are cyclopentyl,
cyclohexyl, cycloheptyl and cyclooctyl; [0296] an example of
C.sub.7-C.sub.9phenylalkyl is benzyl; and [0297] examples of
alkylene are ethylene, propylene, trimethylene, tetramethylene,
pentamethylene, 2,2-dimethyltrimethylene, hexamethylene,
trimethylhexamethylene, octamethylene and decamethylene. [0298]
(h') A compound of the formula (1h) ##STR58## in which n.sub.6 is
the number 1 or 2, G and G.sub.11, are as defined under (a'), and
G.sub.14 is as defined under (b'), but G.sub.14 cannot be --CONH--Z
and --CH.sub.2--CH(OH)--CH.sub.2--O--D--O--. [0299] (i') A compound
of the formula (1i) ##STR59## wherein the radicals G.sub.39,
independently of one another, are a group of the formula (1i-1)
##STR60## in which G.sub.40is C.sub.1-C.sub.12alkyl or
C.sub.5-C.sub.12cycloalkyl, G.sub.41 is C.sub.2-C.sub.12alkylene
and G.sub.42 is as defined for G.sub.11 above.
[0300] Alkyl is for example C.sub.1-C.sub.4alkyl, in particular
methyl, ethyl, propyl or butyl.
[0301] Cycloalkyl is preferably cyclohexyl.
[0302] Alkylene is for example ethylene, propylene, trimethylene,
tetramethylene, pentamethylene, 2,2dimethyltrimethylene or
hexamethylene.
[0303] Alkenyl is preferably allyl.
[0304] Phenylalkyl is preferably benzyl.
[0305] Acyl is preferably acetyl. [0306] (j') A compound of the
formula (1j) ##STR61## wherein G, G.sub.11 are as defined above and
[0307] when n.sub.7 is 1, T.sub.7 is hydrogen,
C.sub.1-C.sub.12alkyl, C.sub.3-C.sub.5alkenyl,
C.sub.7-C.sub.9aralkyl, C.sub.5-C.sub.7cycloalkyl,
C.sub.2-C.sub.4hydroxyalkyl, C.sub.2-C.sub.6alkoxyalkyl,
C.sub.6-C.sub.10aryl, glycidyl, a group of the formula
--(CH.sub.2).sub.t--COO--Q or of the formula
--(CH.sub.2).sub.t--O--CO--Q wherein t is 1 or 2, and Q is
C.sub.1-C.sub.4alkyl or phenyl; or [0308] when n.sub.7 is 2,
T.sub.7 is C.sub.2-C.sub.12alkylene, C.sub.6-C.sub.12arylene, a
group
--CH.sub.2CH(OH)--CH.sub.2--O--X--O--CH.sub.2--CH(OH)--CH.sub.2--
wherein X is C.sub.2-C.sub.10alkylene, C.sub.6-C.sub.15arylene or
C.sub.6-C.sub.12cycloalkylene, or a group
--CH.sub.2CH(OZ')CH.sub.2--(OCH.sub.2--CH(OZ')CH.sub.2).sub.2--
wherein Z' is hydrogen, C.sub.1-C.sub.18alkyl, allyl, benzyl,
C.sub.2-C.sub.12alkanoyl or benzoyl. [0309] (k') A compound of the
formula (1k) ##STR62## wherein G, G.sub.11 are as defined above.
[0310] (l') A compound of the formula (1l) ##STR63## wherein G,
G.sub.11 are as defined above.
[0311] Examples for HALS are the compounds
bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate,
bis(2,2,6,6-tetramethyl-4-piperidyl)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-hydroxybenzylmalonate, the condensate
of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and
succinic acid, linear or cyclic condensates of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-tert-octylamino-2,6-dichloro-1,3,5-triazine,
tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate,
tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate,
1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperazinone),
4-benzoyl-2,2,6,6-tetramethylpiperidine,
4-stearyloxy-2,2,6,6-tetramethylpiperidine,
bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-bu-
tylbenzyl)-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)hexamethylene-diamine 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-triazi-
ne 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-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-d-
ione,
3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione,
3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione,
5-(2-ethylhexanoyl)-oxymethyl-3,3,5-trimethyl-2-morpholinone,
1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperi-
dine,
1,3,5-tris(N-cyclohexyl-N-(2,2,6,6-tetramethylpiperazin-3-on-4-yl)am-
ino)-s-triazine,
1,3,5-tris(N-cyclohexyl-N-(1,2,2,6,6-pentamethylpiperazin-3-on-4-yl)amino-
)-s-triazine, the reaction product of
2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl)butylamino]-6-chloro-s-tr-
iazine with N,N'-bis(3-aminopropyl)ethylenediamine), 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;
5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone; 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)hexamethy-
lenediamine, a diester of 4-methoxymethylenemalonic acid with
1,2,2,6,6-pentamethyl-4-hydroxypiperidine,
poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane,
a reaction product of maleic acid anhydride-.alpha.-olefin
copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or
1,2,2,6,6-pentamethyl-4-aminopiperidine.
[0312] Preferred HALS are of molecular weight 400 g/mol or higher;
especially preferred are oligomeric HALS of the classes mentioned
above, e.g. of molecular weight of 1000 g/mol or higher, e.g.
1500-15000 glmol.
[0313] Especially preferred are those of the alkoxyamine class
(NOR-HALS), e.g. compound H1 as used in the examples below (also
disclosed in Example 2 of U.S. Pat. No. 6,117,995).
[0314] An appropriate combination of the photochromic dyes with UV
absorber and a HALS provides an exceptional improvement of the
long-term photostability, achieving a lifetime thirty times longer
than the unstabilized system.
[0315] The components used in the invention can be pure or mixtures
of compounds.
[0316] Components (c) to be used within present invention basically
are known materials, many are commercially available.
[0317] Optional further ingredients include further stabilizers,
antioxidants, softeners, flame retardants etc. as commonly used for
polymeric material, such as the following components:
1. Antioxidants
[0318] 1.1. Alkylated monophenols, for example
2,6-di-tert-butyl-4-methylphenol, 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-(.alpha.-methylcyclohexyl)-4,6-dimethylphenol,
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'-methylheptadec-1'-yl)phenol,
2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures thereof.
[0319] 1.2. Alkylthiomethylphenols, for example
2,4-dioctylthiomethyl-6-tert-butylphenol,
2,4-dioctylthiomethyl-6-methylphenol,
2,4-dioctylthiomethyl-6-ethylphenol,
2,6-di-dodecylthiomethyl-4-nonylphenol. [0320] 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. [0321] 1.4.
Tocopherols, for example .alpha.-tocopherol, .beta.-tocopherol,
.gamma.-tocopherol, .delta.-tocopherol and mixtures thereof
(vitamin E). [0322] 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-methylphenol)
4,4'-thiobis(3,6-di-sec-amylphenol),
4,4'-bis(2,6-dimethyl-4hydroxyphenyl)-disulfide. [0323] 1.6.
Alkylidenebisphenols, for example
2,2'-methylenebis(6-tert-butyl-4-methylphenol),
2,2'-methylenebis(6-tert-butyl-4-ethylphenol),
2,2'-methylenebis[4-methyl-6-(.alpha.-methylcyclohexyl)-phenol],
2,2'-methylenebis(4-methyl-6-cyclohexylphenol),
2,2'-methylenebis(6-nonyl4-methylphenol),
2,2'-methylenebis(4,6-di-tert-butylphenol),
2,2'-ethylidenebis(4,6-di-tert-butylphenol),
2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol),
2,2'-methylenebis[6-(.alpha.-methylbenzyl)-4-nonylphenol],
2,2'-methylenebis[6-(.alpha.,.alpha.-dimethylbenzyl)-4-nonylphenol],
4,4'-methylenebis(2,6-di-tert-butylphenol),
4,4'-methylenebis(6-tert-butyl-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. [0324]
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-hydroxybenzyl)sulfide,
isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate. [0325]
1.8. Hydroxybenzoate 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. [0326] 1.9. Aromatic hydroxybenzyl compounds,
for example
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenz-
ene,
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. [0327] 1.10.
Triazine compounds, for example
2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triaz-
ine,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-tri-
azine,
2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-t-
riazine,
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.
[0328] 1.11. Benzylphosphonates, for example
dimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate,
diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate,
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-hydroxybenzylphosphonic acid. [0329] 1.12.
Acylaminophenols, for example 4-hydroxylauranilide,
4-hydroxystearanilide, octyl
N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate. [0330] 1.13. Esters
of .beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with
mono- or polyhydric alcohols, e.g. with methanol, ethanol,
n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene
glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. [0331]
1.14. Esters of
.beta.-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with
mono- or polyhydric alcohols, e.g. with methanol, ethanol,
n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol,
ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene
glycol, diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis-(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane;
3,9bis[2-3-{3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimet-
hylethyl]-2,4,8,10-tetraoxaspiro[5.5]-undecane. [0332] 1.15. Esters
of .beta.-(3.5-dicyclohexyl-4-hydroxyyhenyl)propionic acid with
mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,
octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,
1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. [0333]
1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with
mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol,
octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,
1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane. [0334]
1.17. Amides of .beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic
acid e.g.
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenedia-
mide,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediam-
ide, 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). [0335] 1.18. Ascorbic
acid (vitamin C) [0336] 1.19. Aminic antioxidants, for example
N,N'-di-isopropyl-p-phenylenediamine,
N,N'-di-sec-butyl-p-phenylenediamine,
N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine,
N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine,
N,N'-bis(1-methylheptyl)-p-phenylenediamine,
N,N'-dicyclohexyl-p-phenylenediamine,
N,N'-diphenyl-p-phenylenediamine,
N,N'-bis(2-naphthyl)-p-phenylenediamine,
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-isopropoxy-diphenylamine,
N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,
N-phenyl-2-naphthylamine, octylated diphenylamine, for example
p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol,
4-butyrylaminophenol, 4-nonanoylaminophenol,
4-dodecanoyl-aminophenol, 4-octadecanoylaminophenol,
bis(4-methoxyphenyl)amine,
2,6-di-tert-butyl-4-dimethylaminomethylphenol,
2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,
N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane,
1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,
(o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine,
tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and
dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono-
and dialkylated nonyidiphenylamines, a mixture of mono- and
dialkylated dodecyidiphenylamines, a mixture of mono- and
dialkylated isopropyl/isohexyldiphenylamines, a mixture of mono-
and dialkylated tert-butyldiphenylamines,
2,3-dihydro-3,3-dimethyl4H-1,4-benzothiazine, phenothiazine, a
mixture of mono- and dialkylated
tert-butyl/tert-octylphenothiazines, a mixture of mono- and
dialkylated tert-octyl-phenothiazines, N-allylphenothiazine,
N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene,
N,N-bis-(2,2,6,6-tetramethyl-piperid-4-yl-hexamethylenediamine,
bis(2,2,6,6-tetramethylpiperid4-yl)-sebacate,
2,2,6,6-tetramethylpiperidin-4-one,
2,2,6,6-tetramethylpiperidin-4-ol. 2. UV Absorbers and Light
Stabilisers [0337] 2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, for
example 2-(2'-hydroxy-5'-methylphenyl)benzotriazole,
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole,
2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,
2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole,
2-(3',5'-di-tert-butyl-2'-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'-hydroxyphenyl)benzotriazole,
2-(3',5'-bis(.alpha.,.alpha.-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazo-
le,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxyrarbonylethyl)phenyl)-5-chlo-
robenzotriazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)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)benzotriazo-
le,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotr-
iazole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyp-
henyl)benzotriazole,
2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotri-
azole,
2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-yl-
phenol]; 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-butyl4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl,
2-[2'-hydroxy-3'-(.alpha.,.alpha.-dimethylbenzyl)-5'-(1,1,3,3-tetramethyl-
butyl)phenyl]-benzotriazole;
2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(.alpha.,.alpha.-dimethylb-
enzyl)phenyl]benzotriazole. [0338] 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. [0339] 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-hydroxybenzoate,
hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl
3,5-di-tert-butyl4-hydroxybenzoate,
2-methyl-4,6-di-tert-butylphenyl
3,5-di-tert-butyl-4-hydroxybenzoate. [0340] 2.4. Acrylates, for
example ethyl .alpha.-cyano-.beta.,.beta.-diphenylacrylate,
isooctyl .alpha.-cyano-.beta.,.beta.-diphenylacrylate, methyl
.alpha.-carbomethoxycinnamate, methyl
.alpha.-cyano-.beta.-methyl-p-methoxycinnamate, butyl
.alpha.-cyano-.beta.-methyl-p-methoxycinnamate, methyl
.alpha.-carbomethoxy-p-methoxycinnamate and
N-(.beta.-carbomethoxy-.beta.-cyanovinyl)-2-methylindoline. [0341]
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-3,5di-tert-butylbenzylphosphonic acid, nickel complexes
of ketoximes, e.g. of 2-hydroxy4-methylphenylundecylketoxime,
nickel complexes of 1-phenyl4-lauroyl-5-hydroxypyrazole, with or
with-out additional ligands. [0342] 2.6. 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'-ethoxanilide 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. [0343] 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-di-cumylphenyl)pentaerythritol diphosphite,
bis(2,6-di-tert-butyl4-methylphenyl)pentaerythritol diphosphite,
diisodecyloxypentaerythritol diphosphite,
bis(2,4-di-tert-butyl4-methylphenyl)-pentaerythritol diphosphite,
bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite,
tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)
4,4'biphenylene
diphosphonite, 6-isooctyloxy-2,4,8,
10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphosphocin,
bis(2,4-di-tert-butyl-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-dioxaphosphocin,
2,2',2''-nitrilo-[triethyltris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2-
,2'-diyl)phosphite],
2-ethylhexyl(3,3'5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite,
5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane.
[0344] The following phosphites are especially preferred:
Tris(2,4-di-tert-butylphenyl) phosphite (Irgafoso.RTM.168,
Ciba-Geigy), tris(nonylphenyl) phosphite, ##STR64## [0345] 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-octadecylhydroxylamine, N,N-dialkylhydroxylamine
derived from hydrogenated tallow amine. [0346] 6. Nitrones, for
example N-benzyl-alpha-phenyinitrone, N-ethyl-alpha-methyinitrone,
N-octyl-alpha-heptylnitrone, N-lauryl-alpha-undecyinitrone,
N-tetradecyl-alpha-tridecyinitrone,
N-hexadecyl-alpha-pentadecylnitrone,
N-octadecyl-alpha-heptadecyinitrone,
N-hexadecyl-alpha-heptadecylnitrone,
N-ocatadecyl-alpha-pentadecylnitrone,
N-heptadecyl-alpha-heptadecylnitrone,
N-octadecyl-alpha-hexadecylnitrone, nitrone derived from
N,N-dialkylhydroxylamine derived from hydrogenated tallow amine.
[0347] 7. Thiosynergists, for example dilauryl thiodipropionate or
distearyl thiodipropionate. [0348] 8. Peroxide scavengers, for
example esters of .beta.-thiodipropionic acid, for example the
lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole
or the zinc salt of 2-mercaptobenzimidazole, zinc
dibutyidithiocarbamate, dioctadecyl disulfide, pentaerythritol
tetrakis(.beta.-dodecylmercapto)propionate. [0349] 9. Polyamide
stabilisers, for example copper salts in combination with iodides
and/or phosphorus compounds and salts of divalent manganese. [0350]
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. [0351] 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'-dimethylbenzylidene)sorbitol,
1,3:2,4-di(paramethyldibenzylidene)sorbitol, and
1,3:2,4-di(benzylidene)sorbitol. [0352] 12. Fillers and reinforcing
agents, for example calcium carbonate, silicates, glass fibres,
glass beads, 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.
[0353] 13. Other additives, for example plasticisers, lubricants,
emulsifiers, pigments, rheology additives, catalysts, flow-control
agents, optical brighteners, flameproofing agents, antistatic
agents and blowing agents. [0354] 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-butyl-benzofuran-2-one,
5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,
3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one]-
, 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2one,
3-(4-acetoxy-3,5dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,
3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one,
3-(3,4dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one,
3-(2,3-di-methylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.
[0355] Conventional additives such as listed components listed
above under 1.-11. and 14. are often added in concentrations of
from 0.01 to 10%, based on the overall weight of the composition
(components a, b and c). Further additives of items 12. and 13.,
such as fillers or flame retardants, may be contained in much
higher amounts, e.g. from 0.1 to about 50% or even 80% by weight of
the total composition.
[0356] Preferably, the compositions of the present invention do not
contain polyphenolic antioxidants. Such polyphenolic antioxidants
are for example described in U.S. Pat No. 5,770,115.
[0357] The polymeric material usually contains 0.001 to 10% by
weight, most preferably 0.01 to 5% by weight of the stabilizer
component (c). The polymeric material can contain mixtures of two
or more of the HALS (ii) and/or the hydroxyphenyl UV absorber
(i).
[0358] The amount of photochromic dye in the polymeric material
usually is in the range of about 0.001 to 10% by weight, most
preferably 0.01 to 5% by weight, with respect to the total weight
of the polymeric material. The polymeric material can contain
mixtures of two or more photochromic dyes.
[0359] The ratio of component (c) to component (b) can e.g. be in
the range of 0.01 to 100 parts, preferably 0.1 to 10 parts, of
stabilizer (c) per part of photochromic dye (b).
[0360] The ratio of UVA component (i) to HALS component (ii) can
e.g. be in the range of 0.01 to 100 parts, most preferably 0.1 to 2
parts, of UV absorber (i) per part of HALS (ii).
[0361] The polymeric material, the dye (b) and the stabilizer
components (c) often form a homogenous mixture. For specific
applications, however, compositions can be made in which components
(b) and especially (c) are enriched in a part of the polymeric
material, e.g. in the surface areas, or wherein the UV absorber
component (i) is enriched in the surface areas while the remaining
components are mixed homogenously. Of specific technical importance
are 2- or multilayer systems wherein the UV absorber (i) is
enriched in an upper layer containing no photochromic dye, while a
lower layer contains the dye (b) and HALS (ii), and the UV absorber
merely as an optional component. These systems may be obtained by
conventional techniques, e.g. coextrusion, adhesion or stacking of
layers containing UV absorber (i) or UV absorber (i) and HALS (ii)
on one hand, and HALS (ii) and dye (b) on the other hand, and
possible further layers, which may improve further properties such
as scratch resistance, surface gloss and reflection, adhesion, base
colour etc.
[0362] The additives/components of the invention and optional
further components may be added to the polymer material
individually or mixed with one another. If desired, the individual
components can be mixed with one another before incorporation into
the polymer for example by dry blending, compaction or in the
melt.
[0363] The incorporation of the components of the invention and
optional further components into the polymer is carried out by
known methods such as dry blending in the form of a powder, or wet
mixing in the form of solutions, dispersions or suspensions for
example in an inert solvent, water or oil. The additives of the
invention and optional further additives may be incorporated, for
example, before or after molding or also by applying the dissolved,
melted (soaking process) or dispersed additve or additive mixture
to the polymer material, with or without subsequent evaporation of
the solvent or the suspension/dispersion agent. They may be added
directly into the processing apparatus (e.g. extruders, internal
mixers, etc), e.g. as a dry mixture or powder or as solution or
dispersion or suspension or melt.
[0364] The incorporation can be carried out in any heatable
container equipped with a stirrer, e.g. in a closed apparatus such
as a kneader, mixer or stirred vessel. The incorporation is
preferably carried out in an extruder or in a kneader. It is
immaterial whether processing takes place in an inert atmosphere or
in the presence of oxygen.
[0365] The addition of the additive or additive blend to the
polymer can be carried out in all customary mixing machines in
which the polymer is melted and mixed with the additives. Suitable
machines are known to those skilled in the art. They are
predominantly mixers, kneaders and extruders.
[0366] The process is preferably carried out in an extruder by
introducing the additive during processing.
[0367] Particularly preferred processing machines are single-screw
extruders, contrarotating and corotating twin-screw extruders,
planetary-gear extruders, ring extruders or cokneaders. It is also
possible to use processing machines provided with at least one gas
removal compartment to which a vacuum can be applied.
[0368] Suitable extruders and kneaders are described, for example,
in Handbuch der Kunststoffextrusion, Vol. 1 Grundlagen, Editors F.
Hensen, W Knappe, H. Potente, 1989, pp. 3-7, ISBN:3-446-14339-4
(Vol. 2 Extrusionsanlagen 1986, ISBN 3-446-14329-7).
[0369] For example, the screw length is 1-60 screw diameters,
preferably 35-48 screw diameters. The rotational speed of the screw
is preferably 10-600 rotations per minute (rpm), very particularly
preferably 25-300 rpm.
[0370] The maximum throughput is dependent on the screw diameter,
the rotational speed and the driving force. The process of the
present invention can also be carried out at a level lower than
maximum throughput by varying the parameters mentioned or employing
weighing machines delivering dosage amounts.
[0371] Components to be added can be premixed or added
individually.
[0372] The additives/components of the invention and optional
further additives can also be sprayed onto the polymer material.
They are able to dilute other additives (for example the
conventional additives indicated above) or their melts so that they
can be sprayed also together with these additives onto the
material. Addition by spraying during the deactivation of the
polymerization catalysts is particularly advantageous; in this
case, the steam evolved may be used for deactivation of the
catalyst. In the case of spherically polymerized polyolefins it
may, for example, be advantageous to apply the additives of the
invention, optionally together with other additives, by
spraying.
[0373] The components of the invention and optional further
additives can also be added to the polymer in the form of a
concentrate, e.g. a masterbatch, which contains the components in a
concentration of, for example, about 1% to about 40% and preferably
2% to about 20% by weight incorporated in a polymer. The polymer
must not be necessarily of identical structure than the polymer
where the additives are added finally. In such operations, the
polymer can be used in the form of powder, granules, solutions,
suspensions or in the form of latices.
[0374] Incorporation can take place prior to or during the shaping
operation, or by applying the dissolved, melted (soaking process)
or dispersed compound to the polymer, with or without subsequent
evaporation of the solvent. In the case of elastomers, these can
also be stabilized as latices. A further possibility for
incorporating the additives of the invention into polymers is to
add them before, during or directly after the polymerization of the
corresponding monomers or prior to crosslinking. In this context
the additive of the invention can be added as it is or else in
encapsulated form (for example in waxes, oils or polymers).
[0375] The materials containing the additives/components of the
invention described herein can be used for the production of
moldings, rotomolded articles, injection molded articles, blow
molded articles, films, tapes, mono-filaments, fibers, nonwovens,
profiles, adhesives or putties, surface coatings and the like.
[0376] The invention also pertains to a process for stabilizing a
photochromic system containing a photochromic dye in a polymer
matrix against colour fading induced by irradiation, which process
comprises incorporation of a hydroxyphenyl triazine UV absorber and
optionally a sterically hindered amine light stabilizer into the
polymer matrix and/or into a polymer layer covering said polymer
matrix, as well as to the use of a hydroxyphenyl triazine UV
absorber and optionally a sterically hindered amine for improving
the stability of a photochromic system containing a photochromic
dye in a polymer matrix. Preferred processes and uses are in
analogy to the compositions described further above or in the
examples.
[0377] Percentages refer to weight percentages except otherwise
stated.
Materials used in the examples:
[0378] compound UV1 is of the formula ##STR65## [0379] Compound
HALS H1 is of the formula ##STR66## [0380] Compound HALS H2 is of
the formula ##STR67## [0381] Chromene1 is of the formula ##STR68##
[0382] Chromene 2 is of the formula ##STR69##
EXAMPLES
Example 1
[0383] Each compound reported in the table below is mixed in a
turbo mixer with EVA (ethylene-vinylacetate copolymers)
Greenflex.RTM. ML30 pellets (containing 9% of vinyl acetate,
supplied by Polimeri Europa, Italy), characterized by a melt flow
index of 2.5 (190.degree. C./16 Kg; ASTM D1238). TABLE-US-00001 EVA
Chromene1 HALS H1 Formulation g g % g % 1 1998 2 0.1 -- -- 2 1992 2
0.1 6 0.3
[0384] The mixtures are blow extruded (using a mono layer Formac
Lab. 25 blow extruder) at 160.degree. C. and films of 200 micron
thickness are obtained.
[0385] The films thus prepared are mounted on a white card and
exposed outdoor in the sunshine; a film with formulation 1 covered
with a 150 micron thickness film containing 0.15% of the UV
absorber UV1 is exposed in the same conditions (formulation: 1 plus
UV1).
[0386] The covering film is a LDPE film containing as the only
added additive 0.15% of UV1. The covering film is prepared by
mixing 15 g of UV1 and 9850 g of LDPE Riblene FF 29 supplied by
Polimeri Europa; they are mixed in a `turbomixer` for 10 minutes
and blow extruded with a Dolci extruder operating at 210.degree.
C.
[0387] The table below shows the performance of the three sample
films as regards the persistency of the color after light
irradiation: the stabilizing effect of UV1 on the chromene1 itself
and on the chromene1 mixed with HALS H1 is evident. TABLE-US-00002
Formulation KJ/m2 1 42 1 plus UV1 198 2 plus UV1 1250
Example 2
[0388] The formulations are prepared as in example 1 but with a
different chromene. The formulation compositions and results are
shown in the tables below. TABLE-US-00003 EVA Chromene2 HALS H1
Formulation g g % g % 3 1998 2 0.1 -- -- 4 1992 2 0.1 6 0.3
[0389] TABLE-US-00004 Formulation KJ/m2 3 388 3 plus UV1 626 4 plus
UV1 668
Example 3
[0390] The formulations are prepared as in example 1 but a
different sterically hindered amine is used in this example and UV1
is mixed with the other components, i.e. formulation 7 does not
have a covering film. TABLE-US-00005 EVA Chromene1 HALS H2 UV1
Formulation g g % g % g % 6 1998 2 0.1 -- -- 7 1484.25 1.5 0.1 12
0.8 2.25 0.15
[0391] TABLE-US-00006 Formulation KJ/m2 6 42 7 709
[0392] The examples show that the lifetime of the photochromic
system is dramatically enhanced by the stabilization system of the
invention using a sterically hindered amine in combination with a
hydroxyphenyl triazine UV absorber (i).
* * * * *