U.S. patent application number 13/024404 was filed with the patent office on 2011-06-02 for stabilization of polyether polyol, polyester polyol or polyurethane compositions.
Invention is credited to DIETMAR MADER, Pierre Rota-Graziosi.
Application Number | 20110130492 13/024404 |
Document ID | / |
Family ID | 34971573 |
Filed Date | 2011-06-02 |
United States Patent
Application |
20110130492 |
Kind Code |
A1 |
MADER; DIETMAR ; et
al. |
June 2, 2011 |
STABILIZATION OF POLYETHER POLYOL, POLYESTER POLYOL OR POLYURETHANE
COMPOSITIONS
Abstract
The present invention pertains to compositions comprising (a) a
polyether polyol, a polyester polyol or a polyurethane, (b) a
UV-absorber of formula (I) and/or a hindered amine liaht stabilizer
of formula (II) ##STR00001## wherein R.sub.1 and R.sub.2 are each
independently C.sub.1-C.sub.4alkyl or C.sub.1-C.sub.4alkyoxy, and
(c) at least one further UV-absorber and/or hindered amine light
stabilizer if only one of the components (I) and (II) is present
with the proviso that component (c) is not a compound of formula
(A)-(D) as defined in claim 1.
Inventors: |
MADER; DIETMAR; (Freiburg,
DE) ; Rota-Graziosi; Pierre; (Mulhouse, FR) |
Family ID: |
34971573 |
Appl. No.: |
13/024404 |
Filed: |
February 10, 2011 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
11630230 |
Jun 20, 2007 |
7910642 |
|
|
PCT/EP2005/052843 |
Jun 20, 2005 |
|
|
|
13024404 |
|
|
|
|
Current U.S.
Class: |
524/102 ;
524/120; 524/153; 524/220 |
Current CPC
Class: |
C08K 5/3435 20130101;
C08K 5/20 20130101; C08K 5/20 20130101; C08K 5/13 20130101; C08K
5/1345 20130101; C08L 75/04 20130101; C08L 75/04 20130101; C08K
5/005 20130101; C08L 75/04 20130101; C08K 5/3435 20130101 |
Class at
Publication: |
524/102 ;
524/220; 524/120; 524/153 |
International
Class: |
C08K 5/3435 20060101
C08K005/3435; C08K 5/20 20060101 C08K005/20; C08K 5/52 20060101
C08K005/52 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 30, 2004 |
EP |
04103062.8 |
Sep 15, 2004 |
EP |
04104456.1 |
Claims
1. A composition comprising (a) a polyether polyol, a polyester
polyol or a polyurethane, (b) a UV-absorber of formula (I) and/or a
hindered amine light stabilizer of formula (II) ##STR00040##
wherein R.sub.1 and R.sub.2 are each independently
C.sub.1-C.sub.4alkyl or C.sub.1-C.sub.4alkyoxy, and (c) at least
one further hindered amine light stabilizer and/or UV-absorber
selected from the group consisting of hydroxyphenyl-triazine,
benzophenone, oxanilide, acrylate and cyanacrylate classes if only
one of the components (I) and (II) is present with the proviso that
component (c) is not a compound of formula (A)-(D) ##STR00041##
2. A composition according to claim 1, comprising as component (c)
a hindered amine light stabilizer of formula HA-1 to HA-11 or a
UV-absorber of formula UV-5 to UV-8 ##STR00042## ##STR00043##
##STR00044## HA-11)
7-oxa-3,20-diazadispiro[5.1.11.2]heneicosan-21-one,
2,2,4,4-tetramethyl-20-(oxiranylmethyl)--, polymer with
(chloromethyl)oxirane ##STR00045##
3. A composition according to claim 1, comprising further
additives.
4. A composition according to claim 1, comprising further
stabilizers.
5. A composition according to claim 4, comprising as further
stabilizers antioxidants, light-stabilizers and/or processing
stabilizers.
6. A composition according to claim 5, comprising as further
stabilizers phenolic and/or aminic antioxidants, hindered amine
light stabilizers, UV-absorbers, phosphites, phosphonites and/or
benzofuranones.
7. A composition according to claim 6, comprising as further
stabilizers hindered amine light stabilizers, UV-absorbers,
phenolic antioxidants and/or phosphites.
8. A composition according to claim 1, wherein component (b) is a
combination of a UV-absorber of formula (I) and a hindered amine
light stabilizer of formula (II).
9. A composition according to claim 1, wherein the UV-absorber of
formula (I) is a compound of formula (Ia) ##STR00046##
10. A composition according to claim 1, wherein component (b) is a
UV-absorber of formula (I) and component (c) is a hindered amine
light stabilizer.
11. A composition according to claim 1, wherein component (b) is a
hindered amine light stabilizer of formula (II) and component (c)
is a UV-absorber.
12. A composition according to claim 1, wherein the overall amount
of component (b) and (c) is 0.01% to 5%, based on the weight of the
composition.
13. A composition according to claim 1, wherein the overall amount
of component (b) and (c) is 0.5% to 2%, based on the weight of the
composition.
14. A composition according to claim 1, wherein the ratio of
components (b):(c) or of the compounds of formulae (I):(II)
respectively is from 10:1 to 1:10.
15. A composition according to claim 1, wherein the ratio of
components (b):(c) or of the compounds of formulae (I):(II)
respectively is from 3:1 to 1:3.
16. A process for stabilizing a polyether polyol, a polyester
polyol or a polyurethane against degradation by light, oxygen
and/or heat, which process comprises incorporating therein a
mixture of components (b) and (c) as defined in claim 1.
17. A process according to claim 16, whereby the mixture
additionally comprises further additives and/or further
stabilizers.
18. A composition according to claim 6, comprising as further
stabilizers hindered amine light stabilizers, UV-absorbers,
phenolic antioxidants and/or phosphites; the phosphites being
selected from the group consisting of ##STR00047##
Description
[0001] This application is a continuation of application Ser. No.
11/630,230, pending, which is a national stage of international
app. No. PCT/EP 2005/052843, filed Jun. 20, 2005, the contents of
which applications are incorporated herein by reference.
[0002] The present invention pertains to compositions comprising a
polyether polyol, a polyester polyol or a polyurethane susceptible
to light induced degradation, and a mixture of at least two
different light stabilizers, one of them being a specific
UV-absorber and/or hindered amine light stabilizer.
[0003] DE 101 48 702 A1 pertains to stabilizer blends comprising an
antioxidant, a HALS compound, a UV-absorber and a phosphorus
compound. The initial yellowness of thermoplastic polyurethane
stabilized with such a blend of stabilizers is not so great.
[0004] WO 03/095543 relates to stabilizer mixtures for polymer
substrates comprising benzylidene-bis-malonates and at least one
compound selected from the group consisting of UV-absorbers,
hindered amine stabilizers, sterically hindered phenols,
organophosphines, organophosphites and organophosphonites. Such
stabilizer mixtures provide protection of polymeric substrates
against the damaging influence of light exposure by long term
storage of polymers.
[0005] EP 0714931 A discloses a mixture of Tinuvin.RTM. 312,
Tinuvin.RTM. 770 and Chimassorb.RTM. 81 in a polyurethane.
[0006] WO 2004/068217 A describes a polyurethane composition
comprising Tinuvin.RTM. 144, Tinuvin.RTM. 765 and Irganox.RTM.
1010.
[0007] WO 03/078148 A relates to a polyurethane composition
comprising Tinuvin.RTM. 144, Tinuvin.RTM. 765 and Uvinul.RTM.
3040.
[0008] There is a strong demand from the polyurethane industry to
have systems with excellent initial color and good light fastness.
This is especially important for the shoe industry where good color
stability is required, e.g. for thermoplastic polyurethane (TPU).
Furthermore, there is a need for non-yellowing or low-yellowing
polyurethane hot melt adhesives and silylated polyurethane (SPUR)
sealants and artificial leather, especially based on aromatic
isocyanates.
[0009] The polyether polyol, polyester polyol or polyurethane
compositions according to the present invention have an excellent
initial color after processing, good light stability and also good
gas fading resistance.
[0010] The present invention pertains to a composition comprising
[0011] (a) a polyether polyol, a polyester polyol or a
polyurethane, [0012] (b) a UV-absorber of formula (I) and/or a
hindered amine light stabilizer of formula (II)
##STR00002##
[0012] wherein R.sub.1 and R.sub.2 are each independently
C.sub.1-C.sub.4alkyl or C.sub.1-C.sub.4alkyoxy, and [0013] (c) at
least one further UV-absorber and/or hindered amine light
stabilizer if only one of the components (I) and (II) is present
with the proviso that component (c) is not a compound of formula
(A)-(D)
##STR00003##
[0014] As evident from this definition, the composition of this
invention must contain either (i) a UV-absorber of formula (I) and
a hindered amine of formula (II); or (ii) a UV-absorber of formula
(I) and a UV-absorber or/and a hindered amine different from
formulae (I) and (II); or (iii) a hindered amine of formula (II)
and a UV-absorber or/and a hindered amine different from formulae
(I) and (II). Of course, also in case (i) further UV-absorbers
or/and hindered amines may be present.
[0015] Of interest is an instant composition that comprises as
component (c) a hindered amine light stabilizer of formula HA-1 to
HA-11 or a UV-absorber of formula UV-1 to UV-8 as defined
below.
[0016] Of particular interest is an instant composition comprising
as component (c) a hindered amine light stabilizer of formula HA-1
to HA-11 or a UV-absorber of formula UV-1 to UV-7.
[0017] In addition to the light stabilizers (b) and/or (c) the
compositions of the instant invention preferably contain further
additives.
[0018] Such further additives may for example be:
[0019] 1. Antioxidants
[0020] 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.
[0021] 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,
2,4-dodecylthiomethyl-6-tert-butylphenol,
2,4-dodecylthiomethyl-6-methylphenol.
[0022] 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.
[0023] 1.4. Tocopherols, for example .alpha.-tocopherol,
.beta.-tocopherol, .gamma.-tocopherol, .delta.-tocopherol and
mixtures thereof (vitamin E).
[0024] 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-4-hydroxyphenyl)-disulfide.
[0025] 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-nonyl-4-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'-hydroxphenyl)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.
[0026] 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.
[0027] 1.8. Hydroxybenzylated malonates, for example
dioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate,
di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate,
di-dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonat-
e,
bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hyd-
roxybenzyl)malonate.
[0028] 1.9. Aromatic hydroxybenzyl compounds, for example
1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene,
1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene,
2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
[0029] 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-hydroxyphenylpropionyl)-hexahydro-1,3,5-tr-
iazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzypisocyanurate.
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.
[0030] 1.12. Acylaminophenols, for example 4-hydroxylauranilide,
4-hydroxystearanilide, octyl
N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
[0031] 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,
trimethylol-propane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0032] 1.14. Esters of
.beta.-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with
mono- or poly-hydric 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;
3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dim-
ethylethyl]-2,4,8,10-tetraoxaspiro[5.5]-undecane.
[0033] 1.15. Esters of
.beta.-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with mono-
or polyhydric alcohols, e.g. with methanol, ethanol, octanol,
octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,
1,2-propanediol, neopentyl glycol, thiodiethylene glycol,
diethylene glycol, triethylene glycol, pentaerythritol,
tris(hydroxyethyl)isocyanurate, N, N'-bis(hydroxyethyl)oxamide,
3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol,
trimethylolpropane,
4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
[0034] 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.
[0035] 1.17. Amides of
.beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g.
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethyle-
nediamide,
N,N'-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)trimethyle-
nediamide,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide,
N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxami-
de (Naugard.RTM.XL-1, supplied by Uniroyal).
[0036] 1.18. Ascorbic acid (vitamin C) 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-allyldiphenylamine, 4-isopropoxydiphenylamine,
N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine,
N-phenyl-2-naphthylamine, octylated diphenylamine, for example
p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol,
4-butyrylaminophenol, 4-nonanoylaminophenol,
4-dodecanoylaminophenol, 4-octadecanoylaminophenol,
bis(4-methoxyphenyl)amine,
2,6-di-tert-butyl-4-dimethylaminomethylphenol,
2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane,
N,N,N',N'-tetra-methyl-4,4'-diaminodiphenylmethane,
1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane,
(o-tolyl)biguanide, bis[4-(1',3'-dimethylbutyl)phenyl]amine,
tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and
dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono-
and dialkylated nonyldiphenylamines, a mixture of mono- and
dialkylated dodecyldiphenylamines, a mixture of mono- and
dialkylated isopropyl/isohexyldiphenylamines, a mixture of mono-
and dialkylated tert-butyldiphenylamines,
2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a
mixture of mono- and dialkylated
tert-butyl/tert-octylphenothiazines, a mixture of mono- and
dialkylated tert-octylphenothiazines, N-allylphenothiazine,
dinonylphenothiazine, mono-nonylphenothiazine, a mixture of mono-
and dialkylated nonylphenothiazine,
N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene, a mixture of one of the
above disclosed unsubstituted or substituted diphenylamine with one
of the above disclosed unsubstitutued or substituted
phenothiazine.
[0037] 2. Other UV Absorbers and Light Stabilizers
[0038] 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'-hygroxy-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'-hydroxphenyl)benzotriazole,
2-(3',5'-bis(.alpha.,.alpha.-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazo-
le,
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)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-octylmcarbonylethyl)phenyl)benzotria-
zole,
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphe-
nyl)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;
##STR00004##
where R=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl,
2-[2'-hydroxy-3'-(.alpha.,.alpha.-dimethylbenzyl)-5'-(1,1,3,3-tetramethyl-
butyl)phenyl]-benzotriazole;
2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(.alpha.,.alpha.-dimethylb-
enzyl)phenyl]benzotriazole.
[0039] 2.1a. 4-Hydroxybenzoates, for example
2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate,
3,5-di-tert-butyl-4-hydroxybenzoate.
[0040] 2.2. 2-Hydroxybenzophenones and Formamidines, for example
the 4-hydroxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy,
4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy benzophenones;
N-alkyl-N,N'-diarylformamidines, for example, benzoic acid,
4-[[(methylphenylamino)methylene]amino] ethyl ester [Tinuvin 101
(RTM), Ciba Specialty Chemicals Inc.]; benzoic acid,
4-[[(ethylphenylamino)methylene]amino] ethyl ester; 2-propenoic
acid, 3-(4-methoxyphenyl)-, 2-ethylhexyl ester [Uvinul 3088 (RTM),
BASF]; 2-propenoic acid, 2-cyano-3,3-diphenyl-, ethyl ester [Uvinul
3035 (RTM), BASF]; or 2-propenoic acid, 2-cyano-3,3-diphenyl-,
2-ethylhexyl ester [Uvinul 3039 (RTM), BASF].
[0041] 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-butyl-4-hydroxybenzoate,
2-methyl-4,6-di-tert-butylphenyl
3,5-di-tert-butyl-4-hydroxybenzoate.
[0042] 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.
[0043] 2.5. Nickel compounds, for example nickel complexes of
2,2'-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1
or 1:2 complex, with or without additional ligands such as
n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel
dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g.
the methyl or ethyl ester, of
4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes
of ketoximes, e.g. of 2-hydroxy-4-methylphenylundecylketoxime,
nickel complexes of 1-phenyl-4-Iauroyl-5-hydroxypyrazole, with or
without additional ligands.
[0044] 2.6. Further hindered amine light stabilizers, for example
bis(2,2,6,6-tetramethyl-4-piperidyl)succinate,
bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, 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-piperidyphexamethylenediamine and
4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of
2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triaz-
ine and 1,2-bis(3-aminopropylamino)ethane, the condensate of
2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-tri-
azine and 1,2-bis(3-aminopropylamino)ethane,
8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-d-
ione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyr
rolidine-2,5-dione,
3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione,
a mixture of 4-hexadecyloxy- and
4-stearyloxy-2,2,6,6-tetramethylpiperidine, a condensate of
N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and
4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, a condensate of
1,2-bis(3-aminopropylamino)ethane and
2,4,6-trichloro-1,3,5-triazine as well as
4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.
[136504-96-6]); a condensate of 1,6-hexanediamine and
2,4,6-trichloro-1,3,5-triazine as well as N,N-dibutylamine and
4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No.
[192268-64-7]);
N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide,
N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide,
2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4,5]decane,
a reaction product of
7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decane
and epichlorohydrin,
1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenype-
thene,
N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethyl-
enediamine, 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-a-olefin copolymer with
2,2,6,6-tetramethyl-4-aminopiperidine or
1,2,2,6,6-pentamethyl-4-aminopiperidine; HA-6) as defined
below.
[0045] 2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide,
2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxanilide,
2,2'-didodecyloxy-5,5'-di-tert-butoxanilide,
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.
[0046] 2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines, for example
2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-
,
2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,
2,4-bis(2-hydroxy-4-propyloxphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine-
,
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine,
2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazi-
ne,
2-(2-hydroxy-4-tridecyloxwhenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-tri-
azine,
2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-dim-
ethyl)-1,3,5-triazine,
2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethy-
l)-1,3,5-triazine,
2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2-
,4-dimethylphenyl)-1,3,5-triazine,
2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethy-
l-phenyl)-1,3,5-triazine,
2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,
2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,
2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,
2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,
2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis-
(2,4-dimethylphenyl)-1,3,5-triazine.
[0047] 3. Metal deactivators, for example N,N'-diphenyloxamide,
N-salicylal-N'-salicyloyl hydrazine, N,N'-bis(salicyloyl)hydrazine,
N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyphydrazine,
3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl
dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl
bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide,
N,N'-bis(salicyloyl)oxalyl dihydrazide,
N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
[0048] 4. Phosphites and phosphonites, for example triphenyl
phosphite, diphenylalkyl phosphites, phenyldialkyl phosphites,
tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl
phosphite, distearylpentaerythritol diphosphite,
tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol
diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol
diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite,
bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite,
diisodecyloxypentaerythritol diphosphite,
bis(2,4-di-tert-butyl-6-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-dioxaphosph-
ocin , 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-dioxaphosp-
hocin,
2,2',2''-nitrilo-[triethyltris(3,3',5,5'-tetra-tert-butyl-1,1'-biph-
enyl-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.
[0049] 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.
[0050] 6. Nitrones, for example N-benzyl-alpha-phenylnitrone,
N-ethyl-alpha-methylnitrone, N-octyl-alpha-heptylnitrone,
N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone,
N-hexadecyl-alpha-pentadecylnitrone,
N-octadecyl-alpha-heptadecylnitrone,
N-hexadecyl-alpha-heptadecylnitrone,
N-ocatadecyl-alpha-pentadecylnitrone,
N-heptadecyl-alpha-hepta-decylnitrone,
N-octadecyl-alpha-hexadecylnitrone, nitrone derived from
N,N-dialkylhydroxylamine derived from hydrogenated tallow
amine.
[0051] 7. Thiosynergists, for example dilauryl thiodipropionate or
distearyl thiodipropionate.
[0052] 8. Peroxide scavengers, for example esters of
.beta.-thiodipropionic acid, for example the lauryl, stearyl,
myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt
of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate,
dioctadecyl disulfide, pentaerythritol
tetrakis((.beta.-dodecylmercapto)propionate.
[0053] 9. Basic co-stabilisers, for example melamine,
polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea
derivatives, hydrazine derivatives, amines, polyamides,
polyurethanes, alkali metal salts and alkaline earth metal salts of
higher fatty acids, for example calcium stearate, zinc stearate,
magnesium behenate, magnesium stearate, sodium ricinoleate and
potassium palmitate, antimony pyrocatecholate or zinc
pyrocatecholate.
[0054] 10. Fillers and reinforcing agents, for example calcium
carbonate, silicates, glass fibres, glass bulbs, asbestos, talc,
kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon
black, graphite, wood flour and flours or fibers of other natural
products, synthetic fibers.
[0055] 11. Other additives, for example plasticisers, lubricants,
emulsifiers, pigments, rheology additives, catalysts, flow-control
agents, optical brighteners, flameproofing agents, antistatic
agents and blowing agents.
[0056] 12. 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;
EP-A-0591102 or EP-A-1291384 or
3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one,
5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one,
3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)-benzofuran-2-one-
], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one,
3-(4-acetm-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,
3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one,
3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one,
3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one or
3-(2-acetyl-5-isooctylphenyl)-5-isooctylbenzofuran-2-one.
[0057] 13. Anti-gas fading agents, for example
1,1,1',1'-tetramethyl-4,4'-(methylene-di-p-phenylene)disemicarbazide;
1,6-hexamethylene bis(N,N-dimethylsemicarbazide);
11-[6-[[(2,2-dimethylhydrazino)carbonyl]amino]hexyl]-10,12-dioxo-,
bis(2 ,2-d imethylhydrazide).
[0058] The further additives are added, for example, in
concentrations of 0.01 to 10%, relative to the total weight of the
composition of this invention.
[0059] Preferably, such further stabilizers are antioxidants,
further light-stabilizers and/or processing stabilizers.
[0060] More preferably, such further stabilizers are phenolic
and/or aminic antioxidants, further hindered amine light
stabilizers, further UV-absorbers, phosphites, phosphonites and/or
benzofuranones.
[0061] Of outstanding interest are compositions, where the further
stabilizers are further hindered amine light stabilizers, further
UV-absorbers, phenolic antioxidants and/or phosphites.
[0062] Of interest are also such compositions, wherein component
(b) is a combination of a UV-absorber of formula (I) and a hindered
amine light stabilizer of formula (II).
[0063] Preferred are compositions, wherein the UV-absorber of
formula (I) is a compound of formula (Ia).
##STR00005##
[0064] An embodiment of the present invention is a composition,
wherein component (b) is a UV-absorber of formula (I) and component
(c) is a hindered amine light stabilizer.
[0065] Another embodiment of the present invention is a
composition, wherein component (b) is a hindered amine light
stabilizer of formula (II) and component (c) is a UV-absorber.
[0066] Of interest are compositions, wherein the overall amount of
component (b) and (c) is 0.01% to 5%, based on the weight of the
composition.
[0067] Of special interest are compositions, wherein the overall
amount of component (b) and (c) is 0.5% to 2%, based on the weight
of the composition.
[0068] Preferred are compositions, wherein the ratio of components
(b):(c) or of the compounds of formulae (I):(II) respectively is
from 10:1 to 1:10.
[0069] Most preferred are compositions, wherein the ratio of
components (b):(c) or of the compounds of formulae (I):(II)
respectively is from 3:1 to 1:3.
[0070] Preferably, the compositions according to this invention do
not contain benzylidene-bis-malonates. Such
benzylidene-bis-malonates are disclosed in WO 03/095543.
[0071] The present invention also pertains to the use of a mixture
of component (b) and (c) as defined herein as stabilizer for a
polyether polyol, a polyester polyol or a polyurethane against
degradation by light, oxygen and/or heat.
[0072] Preferred is the use of such mixtures that additionally
comprise further additives and/or stabilizers. The further
additives and/or stabilizers may be as defined herein.
[0073] The present invention also pertains to a process for
stabilizing a polyether polyol, a polyester polyol or a
polyurethane against degradation by light, oxygen and/or heat,
which process comprises incorporating into said material a mixture
of component (b) and (c) as defined herein.
[0074] Preferred is a process for stabilizing a polyether polyol, a
polyester polyol or a polyurethane against degradation by light,
oxygen and/or heat, which process comprises incorporating into said
material a mixture comprising component (b) and (c) as defined
herein and additionally comprises further additives and/or
stabilizers. The further additives and/or stabilizers may be as
defined herein.
[0075] Hindered amine light stabilizers are preferably compounds
containing at least one group of formula (III)
##STR00006##
wherein G.sub.1 and G.sub.2 are independently alkyl of 1 to 4
carbon atoms, or G.sub.1 and G.sub.2 together are pentamethylene;
preferably G.sub.1 and G.sub.2 are each methyl. specifies the
border of a chemical group and does not have a chemical meaning by
itself.
[0076] The hindered amine light stabilizers useful as component (c)
may be the ones mentioned in 2.6. herein above and the ones
disclosed in WO 01/62836, WO 02/02706 and DE 10008367, which are
incorporated here by reference.
[0077] Preferred hindered amine light stabilizers are compounds of
formulae (100)-(104) or
7-Oxa-3,20-diazadispiro[5.1.11.2]heneicosan-21-one,
2,2,4,4-tetramethyl-20-(oxiranylmethyl)-, polymer with
(chloromethyl)oxirane;
##STR00007##
wherein
[0078] E is hydrogen, C.sub.1-C.sub.18alkyl, C.sub.1-C.sub.18alkoxy
or C.sub.1-C.sub.18alkoxy substituted by 1 OH;
[0079] n.sub.1 is 1 or 2;
[0080] when n.sub.1 is 1, R.sub.3 is C.sub.1-C.sub.25alkyl or
--CO--R.sub.10;
[0081] when n.sub.1 is 2, R.sub.3 is C.sub.2-C.sub.14alkylene or
--CO--R.sub.11--CO--;
[0082] R.sub.10 is C.sub.1-C.sub.23alkyl;
[0083] R.sub.11 is C.sub.2-C.sub.14-alkylene;
[0084] n.sub.2 is 2 to 4;
[0085] n.sub.3 is 1 to 3,
[0086] R.sub.5 is hydrogen or C.sub.1-C.sub.12alkyl;
[0087] R.sub.4 is the group T.sub.1,
[0088] T.sub.1 is
##STR00008##
[0089] n.sub.4 is 2 to 8,
[0090] n.sub.5 is 1 to 50;
[0091] R.sub.6 is morpholino, piperidino, 1-piperizinyl, alkylamino
of 1 to 8 carbon atoms, especially branched alkylamino of 3 to 8
carbon atoms such as tert-octylamino, --N(alkyl)T.sub.2 with alkyl
of 1 to 8 carbon atoms, or --N(alkyl).sub.2 of 2 to 16 carbon
atoms,
[0092] T.sub.2 is
##STR00009##
[0093] R.sub.7 is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl
substituted by alkyl of 1 to 4 carbon atoms, s-triazinyl
substituted once by chlorine and once by R.sub.6, or s-triazinyl
substituted twice by R.sub.6 with the condition that the two
R.sub.6 substituents may be different;
[0094] R.sub.8 is chlorine, amino substituted by alkyl of 1 to 8
carbon atoms or by T.sub.2, --N(alkyl)T.sub.2 with alkyl of 1 to 8
carbon atoms, --N(alkyl).sub.2 of 2 to 16 carbon atoms, or the
group T.sub.3,
[0095] T.sub.3 is
##STR00010##
[0096] R.sub.12 is hydrogen, acyl of 2 to 4 carbon atoms, carbamoyl
substituted by alkyl of 1 to 4 carbon atoms, s-triazinyl
substituted twice by --N(alkyl).sub.2 of 2 to 16 carbon atoms or
s-triazinyl substituted twice by --N(alkyl)T.sub.2 with alkyl of 1
to 8 carbon atoms;
[0097] A.sub.l is hydrogen or C.sub.1-C.sub.4alkyl,
[0098] A.sub.2 is a direct bond or C.sub.1-C.sub.10alkylene,
[0099] A.sub.3 is C.sub.1-C.sub.4alkyl or C.sub.1-C.sub.4alkoxy
and
[0100] n.sub.6 is a number from 2 to 50, preferably 2 to 20;
[0101] n.sub.8 is 2 to 12.
[0102] Of particular interest as component (c) are UV-absorbers of
the hydroxyphenyl-triazine, benzotriazole, benzophenone, oxanilide,
acrylate and cyanacrylate classes.
[0103] The hydroxyphenyl triazine UV absorber usually is selected
from known compounds, 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;
preferred are compounds as described in U.S. Pat. No. 5,998,116,
U.S. Pat. No. 6,255,483, U.S. Pat. No. 6,060,543.
[0104] Examples for hydroxyphenyl triazine UV absorbers are
compounds conforming to formula (200), (201) or (202)
##STR00011##
wherein
[0105] X and Y are independently 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 are independently Z.sub.1 or
Z.sub.2;
[0106] R.sub.13 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.17, --SOR.sub.17 or
--SO.sub.2R.sub.17; or said alkyl, said cycloalkyl or said
phenylalkyl substituted by one to three halogen, --R.sub.18,
--OR.sub.19, --N(R.sub.19).sub.2, --COR.sub.19, --COOR.sub.19,
--OCOR.sub.19, --CN, --NO.sub.2, --SR.sub.19, --SOR.sub.19,
--SO.sub.2R.sub.19 or --P(O)(OR.sub.19).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.19--, --CONR.sub.19--, --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;
[0107] R.sub.17 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;
[0108] R.sub.18 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;
[0109] R.sub.19 is defined as is R.sub.18; or R.sub.19 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.19 is a group for
formula
##STR00012##
[0110] T is hydrogen, oxyl, hydroxyl, --OT.sub.4, alkyl of 1 to 24
carbon atoms, said alkyl substituted by one to three hydroxy;
benzyl or alkanoyl of 2 to 18 carbon atoms;
[0111] T.sub.4 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;
[0112] R.sub.14 is hydrogen, straight or branched chain alkyl of 1
to 24 carbon atoms or cycloalkyl of 5 to 12 carbon atoms or
R.sub.20; or said alkyl or said cycloalkyl substituted by one to
four halogen, hydroxy, epoxy, glycidyloxy, furyloxy, --R.sub.18,
--OR.sub.19, --N(R.sub.19).sub.2, --CON(R.sub.19).sub.2,
--COR.sub.19, --COOR.sub.19, --OCOR.sub.19,
--OCOC(R.sub.19).dbd.C(R.sub.19).sub.2,
--C(R.sub.19).dbd.CCOOR.sub.19, --CN, --NCO, or
##STR00013##
[0113] or combinations thereof; or said alkyl or said cycloalkyl
interrupted by one to four epoxy, --O--, --NR.sub.19--,
--CONR.sub.19--, --COO--, --OCO--, --CO--,
--C(R.sub.19).dbd.C(R.sub.19)COO--,
--OCOC(R.sub.19).dbd.C(R.sub.19)--,
--C(R.sub.19).dbd.C(R.sub.19)--, 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.14 is --SO.sub.2R.sub.17 or
--COR.sub.21;
[0114] R.sub.21 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.22COOH or --NH--R.sub.23--NCO;
[0115] R.sub.22 is alkylene of 2 to 14 carbon atoms or
phenylene;
[0116] R.sub.23 is alkylene of 2 to 24 carbon atoms, phenylene,
tolylene, diphenylmethane or a group
##STR00014##
[0117] R.sub.13, R.sub.15 and R.sub.13'' are the same or different
and are as defined for R.sub.13;
[0118] R.sub.14, R.sub.16 and R.sub.14'' are the same or different
and are as defined for R.sub.14;
[0119] Z.sub.1 is a group of formula
##STR00015##
[0120] Z.sub.2 is a group of formula
##STR00016##
where
[0121] r.sub.13 and r.sub.14 are independetly of each other 0 or
1;
[0122] R.sub.20, R.sub.24, R.sub.25, R.sub.26, R.sub.27, R.sub.28,
R.sub.29, R.sub.30, R.sub.31 and R.sub.32 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.26 and R.sub.27 or R.sub.31 and R.sub.32
together with the phenyl radical to which they are attached are a
cyclic radical interrupted by one to three --O-- or
--NR.sub.19--.
[0123] Examples of hydroxyphenyltriazines are the compounds
(a1)-(a19)
[0124] a1)
2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine,
[0125] a2)
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,-
5-triazine,
[0126] a3)
2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triaz-
ine,
[0127] a4)
2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3-
,5-triazine,
[0128] a5)
2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-tr-
iazine,
[0129] a6)
2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,-
3,5-triazine,
[0130] a7)
2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1-
,3,5-triazine,
[0131] a8)
2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropoxy)phenyl]-4,6-bis(2,4-
-dimethylphenyl)-1,3,5-triazine,
[0132] a9)
2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]-4,6-bis(2-
,4-dimethylphenyl)-1,3,5-triazine,
[0133] a10)
2-(2-hydroxy-4-[2-ethylhexyl]oxyphenyl)-4,6-di(4-phenylphenyl)-1,3,5-tria-
zine,
[0134] a11)
2-(2-hydroxy-4-[2-heptylcarbonyloxyethoxy]phenyl)-4,6-diphenyl-1,3,5-tria-
zine,
[0135] a12)
2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1,3,5-triazine,
[0136] a13)
2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2-
,4-dimethylphenyl)1,3,5-triazine,
[0137] a14)
2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxpropoxy)phenyl]-4,6-bis(2,4-dimethyl-
phenyl)-1,3,5-triazine,
[0138] a15)
2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine,
[0139] a16)
2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine,
[0140] a17)
2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine,
[0141] a18)
2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine,
[0142] a19)
2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis-
(2,4-dimethylphenyl)-1,3,5-triazine.
[0143] Examples of UV-absorber of the benzotriazole class are
compounds of formula (206) and/or (207),
##STR00017##
wherein
[0144] R.sub.33 is hydrogen, halogen, C.sub.1-C.sub.4alkyl or
C.sub.1-C.sub.8alkoxy;
[0145] R.sub.34 is hydrogen, C.sub.1-C.sub.18alkyl or
C.sub.1-C.sub.8alkyl substituted by phenyl;
[0146] R.sub.35 is C.sub.1-C.sub.12alkyl,
--CH.sub.2CH.sub.2--CO--R.sub.37 or C.sub.1-C.sub.8alkyl
substituted by phenyl;
[0147] R.sub.37 is a monovalent polyethylene oxide residue;
[0148] R.sub.36 is a divalent polyethylene oxide residue;
[0149] Examples of benzotriazoles are the compounds (b1)-(b23)
[0150] b1) 2-(2'-hydroxy-6-methylphenyl)benzotriazole,
[0151] b2)
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole,
[0152] b3) 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,
[0153] b4)
2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole-
,
[0154] b5)
2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chlorobenzotriazole,
[0155] b6)
2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriaz-
ole,
[0156] b7)
2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole,
[0157] b8) 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole,
[0158] b9)
2-(3',5'-di-tert-amyl-2'-hydroxyphenyl)benzotriazole,
[0159] b10)
2-(3',5'-bis(a,a-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole,
[0160] b11)
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chlorob-
enzotriazole,
[0161] b12)
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)--
5-chlorobenzotriazole,
[0162] b13)
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobe-
nzotriazole,
[0163] b14)
2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazo-
le,
[0164] b15)
2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriaz-
ole,
[0165] b16)
2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)b-
enzotriazole,
[0166] b17)
2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole,
[0167] b18)
2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotri-
azole,
[0168] b19)
2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol-
],
[0169] b20) the transesterification product of
2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotr-
iazole with polyethylene glycol 300,
[0170] b21)
##STR00018##
where R
=3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazol-2-ylphenyl,
[0171] b22)
2-[2'-hydroxy-3'-(.alpha.,.alpha.-dimethylbenzyl)-5'-(1,1,3,3-tetramethyl-
butyl)phenyl]benzotriazole,
[0172] b23)
2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(.alpha.,.alpha.-dimethylb-
enzyl)phenyl]benzotriazole.
[0173] The phenolic antioxidant may be a compound of formula (300),
(301) or (302)
##STR00019##
[0174] wherein R.sub.38 and R.sub.39 are independently
C.sub.1-C.sub.8alkyl, R.sub.47 is C.sub.1-C.sub.18alkyl;
[0175] or the phenolic antioxidant may be any compound listed in
items 1.1-1.17 in the list of stabilizers given above.
[0176] The phosphite may be a compound of formula (400) or
(401)
##STR00020##
[0177] wherein R.sub.40, R.sub.41, R.sub.42 and R.sub.43 are
independently C.sub.1-C.sub.8alkyl; or R.sub.40 and R.sub.42 may
independently be hydrogen;
[0178] R.sub.44, R.sub.45 and R.sub.46 are independently hydrogen
or C.sub.1-C.sub.8alkyl;
[0179] or the phosphite may be any phosphite compound listed in
item 4 in the list of stabilizers given above.
[0180] The term alkyl may comprise within the limits of the given
number of carbon atoms, for example 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, 2-methylheptyl, 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 or dodecyl.
[0181] In the context of the description of the present invention,
the term alkylene comprises within the limits of the given number
of carbon atoms, for example methylene and the branched and
unbranched isomers of ethylene, propylene, butylene, pentylene,
hexylene, heptylene, octylene, nonylene, decylene, undecylene,
dodecylene, tridecylene and tetradecylene.
[0182] The term alkoxy may comprise within the limits of the given
number of carbon atoms, for example methoxy and ethoxy and the
branched and unbranched isomers of propoxy, butoxy, pentoxy,
hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy,
tridecoxy, tetradecoxy, pentadecoxy, hexadecoxy, heptadecoxy and
octadecoxy.
[0183] The term halogen comprises for example chlorine, bromine and
iodine.
[0184] The term aryl comprises for example phenyl and naphthyl.
[0185] Examples of alkenyl are vinyl, allyl, butenyl, pentenyl,
hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl and
dodecenyl.
[0186] Of special interest are the following hindered amine light
stabilizers:
##STR00021##
[0187] n.sub.7 is 2 to 50, preferably 2 to 20, particular
preference is given to the commercial product TINUVIN.RTM. 622.
##STR00022##
[0188] this compound is described in U.S. Pat. No. 4,477,615;
n.sub.8 is 2 to 12; particular preference is given to the
commercial product UVASORB.RTM. HA-88.
##STR00023##
[0189] n.sub.9 is 2 to 50, preferably 2 to 20, the endgroups
preferably being
##STR00024##
[0190] particular preference is given to the commercial product
CYASORB.RTM. UV-3529.
##STR00025##
[0191] n.sub.10 is 2 to 50, preferably 2 to 20, the endgroups
preferably being
##STR00026##
[0192] particular preference is given to the commercial product
CYASORB.RTM. UV-3346.
##STR00027##
[0193] n.sub.11 is 2 to 50, preferably 2 to 20, with the endgroups
preferably being
##STR00028##
[0194] particular preference is given to the commercial product
CHIMASSORB.RTM. 944.
##STR00029##
[0195] n.sub.12 is 2 to 50, preferably 2 to 20, with the endgroups
preferably being
##STR00030##
[0196] particular preference is given to the commercial product
CHIMASSORB.RTM. 2020.
##STR00031##
[0197] n.sub.14 is 2 to 50, preferably 2 to 20, with the endgroups
preferably being
##STR00032##
[0198] particular preference is given to the commercial product
Tinuvin.RTM. NOR 371.
[0199] HA-11) 7-Oxa-3,20-diazadispiro[5.1.11.2]heneicosan-21-one,
2,2,4,4-tetramethyl-20-(oxiranylmethyl)--, polymer with
(chloromethyl)oxirane, for example
##STR00033##
[0200] n.sub.15 is 2 to 50, for example 2 to 25; the end group
bonded to the nitrogen can be, for example, hydrogen and the end
group bonded to the 2-hydroxypropylene radical can be, for
example,
##STR00034##
[0201] particular preference is given to the commercial product
Hostavin.RTM. N30.
[0202] Of interest are the following UV-absorbers:
##STR00035##
[0203] n.sub.13 is 2 to 20, for example 3 to 10; preferably, this
compound is a mixture of polyethylene glycol and mono- and
diesters; particular preference is given to the commercial product
TINUVIN.RTM. 213.
##STR00036##
[0204] Of particular interest are the UV-absorbers UV-1 to
UV-7.
[0205] Preferably, the phenolic antioxidant is
##STR00037##
[0206] Preferably, phosphite is
##STR00038##
[0207] The additives and stabilizers mentioned herein are mainly
commercially available.
[0208] Preferred embodiements of this invention are a polyether
polyol, a polyester polyol or a polyurethane comprising one of the
following blends of commercially available additives:
[0209] Tinuvin.RTM. 234/Tinuvin.RTM. 144;
[0210] Tinuvin.RTM. 101/Tinuvin.RTM. 144;
[0211] Tinuvin.RTM. 312/Tinuvin 144;
[0212] Tinuvin.RTM. 120/Tinuvin .RTM. 144;
[0213] Tinuvin.RTM. 312/Tinuvin.RTM. 622/Irganox.RTM. 1010;
[0214] Tinuvin.RTM. 312/Tinuvin.RTM. 123/Irganox.RTM. 1010;
[0215] Tinuvin.RTM. 312/Chimassorb.RTM. 119/Irganox.RTM. 1010;
[0216] Tinuvin.RTM. 312/Chimassorb.RTM. 944/Irganox.RTM. 1010;
[0217] Tinuvin.RTM. 312/Chimassorb.RTM. 2020/Irganox.RTM. 1010;
[0218] Tinuvin.RTM. 312/Cyasorb@ UV 3529/Irganox.RTM. 1010;
[0219] Tinuvin.RTM. 312/Cyasorb.RTM. UV 3346/Irganox.RTM. 1010;
[0220] Tinuvin.RTM. 312/Uvasorb.RTM. HA88/Irganox.RTM. 1010;
[0221] Tinuvin.RTM. 312/Tinuvin.RTM. 622/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0222] Tinuvin.RTM. 312/Tinuvin.RTM. 123/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0223] Tinuvin.RTM. 312/Chimassorb.RTM. 119/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0224] Tinuvin.RTM. 312/Chimassorb.RTM. 944/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0225] Tinuvin.RTM. 312/Chimassorb.RTM. 2020/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0226] Tinuvin.RTM. 312/Cyasorb.RTM. UV 3529/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0227] Tinuvin.RTM. 312/Cyasorb.RTM. UV 3346/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0228] Tinuvin.RTM. 312/Uvasorb.RTM. HA88/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0229] Tinuvin.RTM. 312/Tinuvin.RTM. 622/Irganox.RTM. 245;
[0230] Tinuvin.RTM. 312/Tinuvin.RTM. 123/Irganox.RTM. 245;
[0231] Tinuvin.RTM. 312/Chimassorb.RTM. 119/Irganox.RTM. 245;
[0232] Tinuvin.RTM. 312/Chimassorb.RTM. 944/Irganox.RTM. 245;
[0233] Tinuvin.RTM. 312/Chimassorb.RTM. 2020/Irganox.RTM. 245;
[0234] Tinuvin.RTM. 312/Cyasorb.RTM. UV 3529/Irganox.RTM. 245;
[0235] Tinuvin.RTM. 312/Cyasorb.RTM. UV 3346/Irganox.RTM. 245;
[0236] Tinuvin.RTM. 312/Uvasorb.RTM. HA88/Irganox.RTM. 245;
[0237] Tinuvin.RTM. 312/Tinuvin.RTM. 622/Irganox.RTM.
245/Irgafos.RTM. 126;
[0238] Tinuvin.RTM. 312/Tinuvin.RTM. 123/Irganox.RTM.
245/Irgafos.RTM. 126;
[0239] Tinuvin.RTM. 312/Chimassorb.RTM. 119/Irganox.RTM.
245/Irgafos.RTM. 126;
[0240] Tinuvin.RTM. 312/Chimassorb.RTM. 944/Irganox.RTM.
245/Irgafos.RTM. 126;
[0241] Tinuvin.RTM. 312/Chimassorb.RTM. 2020/Irganox.RTM.
245/Irgafos.RTM. 126;
[0242] Tinuvin.RTM. 312/Cyasorb.RTM. UV 3529/Irganox.RTM.
245/Irgafos.RTM. 126;
[0243] Tinuvin.RTM. 312/Cyasorb.RTM. UV 3346/Irganox.RTM.
245/Irgafos.RTM. 126;
[0244] Tinuvin.RTM. 312/Uvasorb.RTM. HA88/Irganox.RTM.
245/Irgafos.RTM. 126;
[0245] Tinuvin.RTM. 312/Tinuvin.RTM. 622/Irganox.RTM. 1726;
[0246] Tinuvin.RTM. 312/Tinuvin.RTM. 123/Irganox.RTM. 1726;
[0247] Tinuvin.RTM. 312/Chimassorb.RTM. 119/Irganox.RTM. 1726;
[0248] Tinuvin.RTM. 312/Chimassorb.RTM. 944/Irganox.RTM. 1726;
[0249] Tinuvin.RTM. 312/Chimassorb.RTM. 2020/Irganox.RTM. 1726;
[0250] Tinuvin.RTM. 312/Cyasorb.RTM. UV 3529/Irganox.RTM. 1726;
[0251] Tinuvin.RTM. 312/Cyasorb.RTM. UV 3346/Irganox.RTM. 1726;
[0252] Tinuvin.RTM. 312/Uvasorb.RTM. HA88/Irganox.RTM. 1726;
[0253] Tinuvin.RTM. 312/Tinuvin.RTM. 622/Irganox.RTM.
1726/Irgafos.RTM. 126;
[0254] Tinuvin.RTM. 312/Tinuvin.RTM. 123/Irganox.RTM.
1726/Irgafos.RTM. 126;
[0255] Tinuvin.RTM. 312/Chimassorb.RTM. 119/Irganox.RTM.
1726/Irgafos.RTM. 126;
[0256] Tinuvin.RTM. 312/Chimassorb.RTM. 944/Irganox.RTM.
1726/Irgafos.RTM. 126;
[0257] Tinuvin.RTM. 312/Chimassorb.RTM. 2020/Irganox.RTM.
1726/Irgafos.RTM. 126;
[0258] Tinuvin.RTM. 312/Cyasorb.RTM. UV 3529/Irganox.RTM.
1726/Irgafos.RTM. 126;
[0259] Tinuvin.RTM. 312/Cyasorb.RTM. UV 3346/Irganox.RTM.
1726/Irgafos.RTM. 126;
[0260] Tinuvin.RTM. 312/Uvasorb.RTM. HA88/Irganox.RTM.
1726/Irgafos.RTM. 126;
[0261] Tinuvin.RTM. 312/Tinuvin.RTM. 144/Irganox.RTM. 1010;
[0262] Tinuvin.RTM. 234/Tinuvin.RTM. 144/Irganox.RTM. 1010;
[0263] Tinuvin.RTM. 101/Tinuvin.RTM. 144/Irganox.RTM. 1010;
[0264] Tinuvin.RTM. 571/Tinuvin.RTM. 144/Irganox.RTM. 1010;
[0265] Tinuvin.RTM. 213/Tinuvin.RTM. 144/Irganox.RTM. 1010;
[0266] Tinuvin.RTM. 328/Tinuvin.RTM. 144/Irganox.RTM. 1010;
[0267] Uvinul.RTM. 3039/Tinuvin.RTM. 144/Irganox.RTM. 1010;
[0268] Uvinul.RTM. 3088/Tinuvin.RTM. 144/Irganox.RTM. 1010;
[0269] Tinuvin.RTM. 120/Tinuvin.RTM. 144/Irganox.RTM. 1010;
[0270] Tinuvin.RTM. 312/Tinuvin.RTM. 144/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0271] Tinuvin.RTM. 234/Tinuvin.RTM. 144/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0272] Tinuvin.RTM. 101/Tinuvin.RTM. 144/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0273] Tinuvin.RTM. 571/Tinuvin.RTM. 144/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0274] Tinuvin.RTM. 213/Tinuvin.RTM. 144/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0275] Tinuvin.RTM. 328/Tinuvin.RTM. 144/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0276] Uvinul.RTM. 3039/Tinuvin.RTM. 144/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0277] Uvinul.RTM. 3088/Tinuvin.RTM. 144/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0278] Tinuvin.RTM. 120/Tinuvin.RTM. 144/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0279] Tinuvin.RTM. 312/Tinuvin.RTM. 144/Irganox.RTM. 245;
[0280] Tinuvin.RTM. 234/Tinuvin.RTM. 144/ Irganox.RTM. 245;
[0281] Tinuvin.RTM. 101/Tinuvin.RTM. 144/ Irganox.RTM. 245;
[0282] Tinuvin.RTM. 571/Tinuvin.RTM. 144/ Irganox.RTM. 245;
[0283] Tinuvin.RTM. 213/Tinuvin.RTM. 144/ Irganox.RTM. 245;
[0284] Tinuvin.RTM. 328/Tinuvin.RTM. 144/ Irganox.RTM. 245;
[0285] Uvinul.RTM. 3039/Tinuvin.RTM. 144/ Irganox.RTM. 245;
[0286] Uvinul.RTM. 3088/Tinuvin.RTM. 144/ Irganox.RTM. 245;
[0287] Tinuvin.RTM. 120/Tinuvin.RTM. 144/ Irganox.RTM. 245;
[0288] Tinuvin.RTM. 312/Tinuvin.RTM. 144/Irganox.RTM.
245/Irgafos.RTM. 126;
[0289] Tinuvin.RTM. 234/Tinuvin.RTM. 144/Irganox.RTM.
245/Irgafos.RTM. 126;
[0290] Tinuvin.RTM. 101/Tinuvin.RTM. 144/Irganox.RTM.
245/Irgafos.RTM. 126;
[0291] Tinuvin.RTM. 571/Tinuvin.RTM. 144/Irganox.RTM.
245/Irgafos.RTM. 126;
[0292] Tinuvin.RTM. 213/Tinuvin.RTM. 144/Irganox.RTM.
245/Irgafos.RTM. 126;
[0293] Tinuvin.RTM. 328/Tinuvin.RTM. 144/Irganox.RTM.
245/Irgafos.RTM. 126;
[0294] Uvinul.RTM. 3039/Tinuvin.RTM. 144/Irganox.RTM.
245/Irgafos.RTM. 126;
[0295] Uvinul.RTM. 3088/Tinuvin.RTM. 144/Irganox.RTM.
245/Irgafos.RTM. 126;
[0296] Tinuvin.RTM. 120/Tinuvin.RTM. 144/Irganox.RTM.
245/Irgafos.RTM. 126;
[0297] Tinuvin.RTM. 312/Tinuvin.RTM. 144/Irganox.RTM. 1726;
[0298] Tinuvin.RTM. 234/Tinuvin.RTM. 144/Irganox.RTM. 1726;
[0299] Tinuvin.RTM. 101/Tinuvin.RTM. 144/Irganox.RTM. 1726;
[0300] Tinuvin.RTM. 571/Tinuvin.RTM. 144/Irganox.RTM. 1726;
[0301] Tinuvin.RTM. 213/Tinuvin.RTM. 144/Irganox.RTM. 1726;
[0302] Tinuvin.RTM. 328/Tinuvin.RTM. 144/Irganox.RTM. 1726;
[0303] Uvinul.RTM. 3039/Tinuvin.RTM. 144/Irganox.RTM. 1726;
[0304] Uvinul.RTM. 3088/Tinuvin.RTM. 144/Irganox.RTM. 1726;
[0305] Tinuvin.RTM. 120/Tinuvin.RTM. 144/Irganox.RTM. 1726;
[0306] Tinuvin.RTM. 312/Tinuvin.RTM. 144/Irganox.RTM.
1726/Irgafos.RTM. 126;
[0307] Tinuvin.RTM. 234/Tinuvin.RTM. 144/Irganox.RTM.
1726/Irgafos.RTM. 126;
[0308] Tinuvin.RTM. 101/Tinuvin.RTM. 144/Irganox.RTM.
1726/Irgafos.RTM. 126;
[0309] Tinuvin.RTM. 571/Tinuvin.RTM. 144/Irganox.RTM.
1726/Irgafos.RTM. 126;
[0310] Tinuvin.RTM. 213/Tinuvin.RTM. 144/Irganox.RTM.
1726/Irgafos.RTM. 126;
[0311] Tinuvin.RTM. 328/Tinuvin.RTM. 144/Irganox.RTM.
1726/Irgafos.RTM. 126;
[0312] Uvinul.RTM. 3039/Tinuvin.RTM. 144/Irganox.RTM.
1726/Irgafos.RTM. 126;
[0313] Uvinul.RTM. 3088/Tinuvin.RTM. 144/Irganox.RTM.
1726/Irgafos.RTM. 126;
[0314] Tinuvin.RTM. 120/Tinuvin.RTM. 144/Irganox.RTM.
1726/Irgafos.RTM. 126.
[0315] More particular preference is given to a polyether polyol, a
polyester polyol or a polyurethane comprising one of the following
blends of commercially available additives:
[0316] Tinuvin.RTM. 312/Tinuvin.RTM. 144
[0317] Tinuvin.RTM. 312/Tinuvin.RTM. 144/Irganox.RTM. 1010;
[0318] Tinuvin.RTM. 312/Tinuvin.RTM. 144/Irganox.RTM. 245;
[0319] Tinuvin.RTM. 312/Tinuvin.RTM. 144/Irganox.RTM.
245/Irgafos.RTM. 126;
[0320] Tinuvin.RTM. 234/Tinuvin.RTM. 144;
[0321] Tinuvin.RTM. 101/Tinuvin.RTM. 144;
[0322] Tinuvin.RTM. 312/Tinuvin.RTM. 144/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0323] Tinuvin.RTM. 234/Tinuvin.RTM. 144/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0324] Tinuvin.RTM. 120/Tinuvin.RTM. 144.
[0325] For example, a polyether polyol, a polyester polyol or a
polyurethane comprises one of the following blends of commercially
available additives:
[0326] TINUVIN.RTM. 234/TINUVIN.RTM. 144/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0327] TINUVIN.RTM. 312/TINUVIN.RTM. 770/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0328] TINUVIN.RTM. 312/TINUVIN.RTM. 622/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0329] TINUVIN.RTM. 312/TINUVIN.RTM. 144/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0330] TINUVIN.RTM. 328/TINUVIN.RTM. 144/Irganox.RTM.
1010/Irgafos.RTM. 126.
[0331] Most preference is given to a polyether polyol, a polyester
polyol or a polyurethane comprising one of the following blends of
commercially available additives:
[0332] Tinuvin.RTM. 312/Tinuvin.RTM. 144/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0333] Tinuvin.RTM. 234/Tinuvin.RTM. 144/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0334] Tinuvin.RTM. 312/Tinuvin.RTM. 144/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0335] Tinuvin.RTM. 312/Tinuvin.RTM. 144/Irganox.RTM. 1010;
[0336] Tinuvin.RTM. 234/Tinuvin.RTM. 144/Irganox.RTM. 1010;
[0337] Tinuvin.RTM. 312/Tinuvin.RTM. 144/Irganox.RTM. 1010.
[0338] Most particular preference is given to a polyether polyol, a
polyester polyol or a polyurethane comprising one of the following
blends of commercially available additives:
[0339] Tinuvin.RTM. 312/Tinuvin.RTM. 144/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0340] Tinuvin.RTM. 234/Tinuvin.RTM. 144/Irganox.RTM.
1010/Irgafos.RTM. 126;
[0341] Tinuvin.RTM. 312/Tinuvin.RTM. 144/Irganox.RTM.
1010/Irgafos.RTM. 126.
[0342] Of special interest is a polyether polyol, a polyester
polyol or a polyurethane comprising the one of the following blends
of commercially available additives:
[0343] Tinuvin.RTM. 312/Tinuvin.RTM. 234/Tinuvin.RTM.
144/Irganox.RTM. 1010/Irgafos.RTM. 126;
[0344] Tinuvin.RTM. 312/Tinuvin.RTM. 234/Tinuvin.RTM.
622/Irganox.RTM. 1010.
[0345] The stabilizers and stabilizer blends mentioned are suitable
as stabilizers for polyether polyol, polyester polyol or
polyurethane against oxidative, thermal and/or light-induced
degradation and as reducer of fogging contribution of the
polymer.
[0346] The polyether polyol, polyester polyol or polyurethane
composition of the present invention may be also a foam (flexible,
rigid, integral), a microcellular foam, a cast PU, a PU skin, a PU
hot melt adhesive, a silylated polyurethane (SPUR), a thermoplasic
polyurethane (TPU) a PU elastomer, artifical leather, PU skin, PU
stray coating or reaction injection molding (RIM).
[0347] For example, polyether polyol, polyester polyol or
polyurethane composition of the present invention are not
foamed.
[0348] The polyurethanes are obtained, for example, by reacting
polyethers, polyesters and polybutadienes which contain terminal
hydroxyl groups, i.e. polyols, with aliphatic or aromatic
polyisocyanates.
[0349] Polyethers and polyesters having terminal hydroxyl groups
are known and are prepared, for example, by polymerizing epoxides
such as ethylene oxide, propylene oxide, butylene oxide,
tetrahydrofuran, styrene oxide or epichlorohydrin with themselves,
for example in the presence of BF.sub.3, or by addition reaction of
these epoxides, alone or as a mixture or in successsion, with
starting components containing reactive hydrogen atoms, such as
alcohols, ammonia or amines, for example ethylene glycol, propylene
1,3- and 1,2-glycol, trimethylolpropane,
4,4'-dihydroxydiphenylpropane, aniline, ethanolamine or
ethylenediamine. Sucrose polyethers are also suitable in accordance
with the invention. In many cases preference is given to those
polyethers which predominantly (up to 90% by weight, based on all
the OH groups present in the polyether) contain primary OH groups.
Furthermore, polyethers modified by vinyl polymers, as are formed,
for example, by polymerizing styrene and acrylonitrile in the
presence of polyethers, are suitable, as are polybutadienes
containing OH groups.
[0350] These compounds generally have molecular weights of 40 and
are polyhydroxy compounds, especially compounds containing from two
to eight hydroxyl groups, especially those of molecular weight from
800 to 10,000, preferably from 1000 to 6000, for example polyethers
containing at least 2, generally 2 to 8, but preferably 2 to 4,
hydroxyl groups, as are known for the preparation of homogeneous
polyurethanes and cellular polyurethanes.
[0351] It is of course possible to employ mixtures of the above
compounds containing at least two isocyanate-reactive hydrogen
atoms, in particular with a molecular weight of 400-10,000.
[0352] Suitable polyisocyanates are aliphatic, cycloaliphatic,
araliphatic, aromatic and heterocyclic polyisocyanates, for example
ethylene diisocyanate, 1,4-tetramethylene diisocyanate,
1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate,
cyclobutane 1,3-diisocyanate, cyclohexane 1,3- and
-1,4-diisocyanate and also any desired mixtures of these isomers,
1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane, 2,4-
and 2,6-hexahydrotolylene diisocyanate and also any desired
mixtures of these isomers, hexahydro-1,3- and/or -1,4-phenylene
diisocyanate, perhydro-2,4'- and/or
-4,4'-diphenylmethanediisocyanate, 1,3-and1,4-phenylene
diisocyanate, 2,4- and 2,6-tolylene diisocyanate, and also any
desired mixtures of these isomers, diphenylmethane 2,4'- and/or
-4,4'-diisocyanate, naphthylene 1,5-diisocyanate, triphenylmethane
4,4',4''-triisocyanate, polyphenyl-polymethylene polyisocyanates as
are obtained by aniline-formaldehyde condensation followed by
phosgenization, m- and p-isocyanatophenylsulfonyl isocyanates,
perchlorinated aryl polyisocyanates, polyisocyanates containing
carbodiimide groups, polyisocyanates containing allophanate groups,
polyisocyanates containing isocyanurate groups, polyisocyanates
containing urethane groups, polyisocyanates containing acylated
urea groups, polyisocyanates containing biuret groups,
polyisocyanates containing ester groups, reaction products of the
above-mentioned isocyanates with acetals, and polyisocyanates
containing polymeric fatty acid radicals.
[0353] It is also possible to employ the isocyanate
group-containing distillation residues as they are or dissolved in
one or more of the above-mentioned polyisocyanates, which are
obtained in the course of the industrial preparation of
isocyanates. It is additionally possible to use any desired
mixtures of the above-mentioned polyisocyanates.
[0354] Particular preference is given in general to the
polyisocyanates which are readily obtainable industrially, for
example aromatic isocyanates such as 2,4- and 2,6-tolylene
diisocyanate and any desired mixtures of these isomers ("TDI"),
polyphenyl-polymethylene-polyisocyanates as prepared by
aniline-formaldehyde condensation followed by phosgenization
("crude MDI"), and polyisocyanates containing carbodiimide,
urethane, allophanate, isocyanurate, urea or biuret groups
("modified polyisocyanates").
[0355] Polyurethane is preferably prepared from liquid starting
components, i.e. the starting materials to be reacted with one
another being mixed together in a one-shot process.
[0356] Incorporation of the additives and/or stabilizer blends into
the polyether polyol, polyester polyol or polyurethane is carried
out by known methods, for example before or during compounding,
extrusion, co-extrusion or can also be added before or during
polymerisation or before crosslinking. In case the additives and/or
stabilizer blends are added before polymerisation, they can be
dissolved in one or all reactants. They are preferably dissolved in
the polyether polyol or polyester polyol.
[0357] The compositions of this invention will help to fulfil needs
and/or requirements for the polyurethane industry, in providing
polyurethane (PU) compounds, thermoplastic PU, cast PU, reaction
injection molding (RIM), spray coating, PU skin.
[0358] The compositions according to the invention can be
advantageously used for various purposes and for the preparation of
various shaped articles. Examples are:
[0359] V) Adhesive, Coating and Elastomer
[0360] V-1) PU Elastomer
[0361] V-1-A) Electrical and Electronic Industry
[0362] Bushes, cable connections, components for electrical control
and adjustment, electromagnetic switches, hard and elastomeric
encapsulants, gear shift cable castings for motor vehicle
electrics, insulants, printed circuits, potting, semiconductors,
switches, switch gears, medium and high voltage transformers.
[0363] V-1-B) Heavy-Duty Industry
[0364] Wheels, conveyor belts, sieves and linings.
[0365] V-1-C) Leisure
[0366] Skate board roller.
[0367] V-2) Adhesives
[0368] V-2-A) Automotive
[0369] Bonding of textile onto foam, direct glazing of vehicle
windscreens, glazing replacement, fastening of various car
components, vacuum lamination of foil to fiberboard.
[0370] V-2-B) Building and Civil Engineering
[0371] Bonding of sandwich insulation panels, flooring, roofs,
sealing of car parks, concrete pavements, industrial floors, one
component sealant for vertical joints (precast concrete panels,
expansion joints), pourable joint sealants for vertical surfaces
(floor-to-wall joints).
[0372] V-2-C) Carpentry
[0373] Furniture assembly and profile lamination of wood to
plastic.
[0374] V-2-D) Flexible Packaging
[0375] Film-to-film and film-to-foil lamination.
[0376] V-2-E) Footwear
[0377] Bonding of shoe soles.
[0378] V-2-F) General Industry
[0379] Electronics industry, household goods, loudspeaker acoustic
panels, office furniture, metal window frames, air conditioning
systems, buses, containers, lorries, metal/sheet metal
constructions, railway carriages, sewerage works, silos and
ventilation systems.
[0380] V-2-G) Insulated Glazing
[0381] V-2-H) Rubbercrumb
[0382] Binding agent for re-milled rubber waste; the composite
materials are mainly used as molded tiles, playgrounds (in-situ),
running tracks (in-situ).
[0383] V-2-J) Sandwich Construction
[0384] Binding of similar substrates together or to other materials
such as metals, plastics and rigid foam; used in a variety of
laminated panels, such as panels for buildings, caravans, partition
walls, refrigerated trucks, containers and cold storages.
[0385] V-3) Polyurethane Hotmelts
[0386] V-3-A) Automotive applications, in particular as instrument
clusters, sound insulation, carpeting, seating, decorative trim,
exterior applications such as weather stripping, exterior trim,
light lens units, and windshield assemblies, recreational vehicle
side walls.
[0387] V-3-B) Textile applications, in particular lamination,
profile wrapping.
[0388] V-3-C) Furniture industry, in particular for bonding bond
solid wood, wood composites, metal hardware, and decorative plastic
laminates.
[0389] V-3-D) Construction industry, in particular assembly of door
and window frames and corner covering for linoleum flooring.
[0390] VI) TPU
[0391] VI-1) Adhesive Grade
[0392] Adhesives for shoe (bond upper to sole), toe caps (powder),
furniture, do it yourself and automotive.
[0393] VI-2) Extrusion Grades
[0394] VI-2-A) Cable and Wire Applications
[0395] Household appliances cables, outdoor electrical cables,
industrial cables and wire.
[0396] VI-2-B) Hoses and Tubes
[0397] Pneumatic transport systems, ventilation systems, pneumatic
control units, pneumatic breaks, hydraulic tubes, corrugated pipes,
fire hoses, vacuum cleaner tubes.
[0398] VI-2-C) Profile Applications
[0399] Round cords, tooth belts, gaskets, bowden cables, stripper
blades, cables.
[0400] VI-3) Film and Sheet
[0401] These are made from both aromatic and aliphatic TPUs.
Typical applications are barrier film, adhesive film, seam tape,
inter layer in security glass.
[0402] VI-3-A) Optical Applications of Aliphatic TPU
[0403] Security laminates, security display screens.
[0404] VI-3-B) Non-Optical Applications of Aliphatic TPU
[0405] Traffic and warning signs, protective films for exterior
automotive applications, industrial tapes, industrial boats and
balloons, film for food packaging, aerospace.
[0406] VI-3-C) Melt Coatings
[0407] Belts for food transportation and industrial goods.
[0408] VI-4) Injection Molding
[0409] VI-4-A) General Purpose
[0410] Ear tags, wheels, horse shoes, plugs, wrist watch
straps.
[0411] VI-4-B) Hi-Performance/Special Compounds
[0412] Transparent soles for sport shoes, frames for ski goggles,
technical parts, screens (mining).
[0413] VI-4-C) Automotive Applications
[0414] Gear shift knobs, bearing sockets, cable plugs, bushings,
casings, friction bearings.
[0415] VI-4-D) Seal Applications
[0416] Hydraulic seals, stripper rings, gaskets, pneumatic seals,
membranes.
[0417] VII) Automotive Applications
[0418] Bumpers, dashboards, battery, rear and front linings,
moldings parts under the hood, hat shelf, trunk linings, interior
linings, air bag covers, electronic moldings for fittings (lights),
panes for dashboards, headlamp glass, instrument panel, exterior
linings, upholstery, automotive lights, head lights, parking
lights, rear lights, stop lights, interior and exterior trims; door
panels; gas tank; glazing front side; rear windows; seat backing,
exterior panels, wire insulation, profile extrusion for sealing,
cladding, pillar covers, chassis parts, exhaust systems, fuel
filter/filler, fuel pumps, fuel tank, body side moldings,
convertible tops, exterior mirrors, exterior trim,
fasteners/fixings, front end module, glass, hinges, lock systems,
luggage/roof racks, pressed/stamped parts, seals, side impact
protection, sound deadener/insulator and sunroof.
[0419] VII-1) Flexible Foam, in particular arm rest, head
restraints, acoustic foam carpet, seats.
[0420] VII-2) Semi-rigid foam, in particular roof liners, hat
racks, door panels, arm rest, instrument panel, head-impact,
side-impact.
[0421] VII-3) Rigid foam, in particular foam filling of
cavities.
[0422] VII-4) Flexible integral foam, in particular steering wheel,
air filter, gearshift knob, spoiler, cable sheeting, head
restraints.
[0423] VII-5) RIM, in particular bumpers, sunroof, front and rear
skirts, door sill scuff plates.
[0424] VII-6) TPU, in particular front and rear skirts, doorsill
scuff plates, cable sheeting, gearshift knob, instrument panel.
[0425] VII-7) Cast PU systems, in particular spring aids, spring
isolation, seat damping, top mounts, roll restrictors, emergency
wheel, body mounts, stops in door systems.
[0426] VIII) Footwear
[0427] Shoes/shoe-soles (insoles, spats, adhesives, structural
adhesives).
[0428] IX) Furniture
[0429] X) Support Devices
[0430] Articles for the leisure time such as sports and fitness
devices, gymnastics mats, ski-boots, inline-skates, skis, big foot,
athletic surfaces (e.g. tennis grounds).
[0431] XI) Others
[0432] Composite panels, insulation board and block, technical
insulation, pipe insulation, food boxes (fruit, vegetables, meat,
fish), synthetic paper, labels for bottles, couches, human
artificial joints, printing plates (flexographic), printed circuit
boards, display technologies, screw tops, tops and stoppers for
bottles, and cans.
[0433] For Example
[0434] 1) PU elastomers
[0435] 2) PU skin
[0436] 3) PU spray coating
[0437] 4) Thermoplastic polyurethane (TPU)
[0438] 5) PU artificial leather
[0439] 6) Silylated polyurethane (SPUR)
[0440] 7) PU hot melt adhesives
[0441] 8) Cast PU
[0442] 9) PU foam (flexible, rigid, integral)
[0443] 10) PU microcelluar
[0444] 11) Reaction injection molding (RIM).
[0445] Thus, a further embodiment of the present invention relates
to a shaped article, in particular artificial leather,
shock-absorbers, rollers of inline-skates and footwear, containing
a composition as described above.
EXAMPLES
##STR00039##
[0447] Percentages and ratios mean weight percent and weight
ratios.
[0448] Compounding:
[0449] 2.5 kg of thermoplastic polyurethane (TPU) pellets
(Desmopan.RTM. 385 S of Bayer Material Science.RTM.) are mixed to
homogeneity in a tumble mixer with 0.33% of pentaerythritol
tetrakis 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate
(Irganox.RTM. 1010), 0.17% of bis(2,4-di-tert-butylphenyl)
pentaerythritol diphosphite (Irgafos.RTM. 126), and with the light
stabilizer combinations given in the tables below. This blend is
then extruded in a twin-screw extruder of Berstorff.RTM. at a
temperature of at most 180.degree. C. After drawing the extrudate
through a waterbath to cool, it is granulated.
[0450] Injection Molding:
[0451] 64 mm.times.40 mm.times.2 mm test panels are moulded from
these granules by means of an injection-moulding machine
(Arburg.RTM. 320 S) at a temperature of at most 180.degree. C.
(mold temperature 50.degree. C.). The samples are exposed in a
Weatherometer (WOM) bpt 63.degree. C., 0.35 W/m2.
[0452] Film Preparation
[0453] 4 g of TPU pellets are dissolved 22 g DMF as a solvent. TPU
films are prepared by drawing film with a 250 micron doctor blade.
The DMF solvent is evaporated and the films are dried. The final
film thickness is about 40 micron.
[0454] Light Expoure
[0455] The samples are exposed in a Weatherometer (WOM) bpt
63.degree. C., 0.35 W/m.sup.2nm at .lamda.=340 nm.
[0456] Kalahari exposure is done according to VW Test PV 3929 with
xenon light exposure at 75 W/m.sup.2 at .lamda.=300-400 nm.
[0457] Color Measurement:
[0458] The color quality is reported in terms of Yellowness Index
(YI) determined on the TPU samples in accordance with the ASTM
1926-70 Yellowness Test. Low YI values denote little discoloration,
high YI values severe discoloration of the samples. The whiter the
TPU the better the TPU is stabilized.
TABLE-US-00001 TABLE 1 Determination of initial color and light
stability obtained with various light stabilizer systems. (Measured
according to ASTM 1926-70). 2 mm plaques, Weatherometer (WOM) bpt
63.degree. C., 0.35 W/m2 Initial Color (YI: yellowness Formulation
% Light stabilizers* index) 72 h 144 h 240 h 316 h 460 h 1 blank
11.9 35.8 49.4 55.9 60.0 66.4 2 0.50% TINUVIN .RTM. 234 14.2 13.8
16.1 20.6 23.9 28.5 0.50% TINUVIN .RTM. 144 3 0.50% TINUVIN .RTM.
312 10.9 12.4 17.6 26.7 34.4 42.1 0.50% TINUVIN .RTM. 622 4 0.50%
TINUVIN .RTM. 312 9.6 9.9 13.7 20.3 25.4 32.8 0.50% TINUVIN .RTM.
144 *All formulations in Table 1 contain 0.33% IRGANOX .RTM. 1010
and 0.17% IRGAFOS .RTM. 126
TABLE-US-00002 TABLE 2 Determination of initial color and light
stability obtained with various light stabilizer systems. (Measured
according to ASTM 1926-70). Film, Weatherometer (WOM) bpt
63.degree. C., 0.35 W/m2 Formulation % Light stabilizers* 15 h 41 h
108 h 5 blank 3.1 6.3 34.1 6 0.50% TINUVIN 234 2.3 3.6 5.5 0.50%
TINUVIN 144 7 0.50% TINUVIN 312 2.7 2.9 5.4 0.50% TINUVIN 622 8
0.50% TINUVIN 312 2.2 3.5 5.5 0.50% TINUVIN 144 *All formulations
in Table 2 contain 0.33% IRGANOX .RTM. 1010 and 0.17% IRGAFOS .RTM.
126
TABLE-US-00003 TABLE 3 Determination of initial color and light
stability obtained with various light stabilizer systems. (Measured
according to ASTM 1926-70). 2 mm plaques, Kalahari exposure (VW
Test PV 3929) Formulation % Light stabilizers* 96 h 144 h 9 blank
53.9 58.7 10 0.50% TINUVIN 234 18.9 22.1 0.50% TINUVIN 144 11 0.33%
TINUVIN 234 23.4 27.0 0.67% TINUVIN 144 12 0.75% TINUVIN 312 16.8
23.3 0.25% TINUVIN 144 13 0.67% TINUVIN 312 17.4 22.6 0.33% TINUVIN
144 14 0.50% TINUVIN 312 18.8 22.3 0.50% TINUVIN 144 15 0.33%
TINUVIN 312 23.4 28.8 0.67% TINUVIN 144 16 0.33% TINUVIN 234 15.9
21.3 0.33% TINUVIN 312 0.33% TINUVIN 144 17 0.25% TINUVIN 234 17.9
23.6 0.25% TINUVIN 312 0.50% TINUVIN 144 18 0.50% TINUVIN 328 19.5
23.4 0.50% TINUVIN 144 19 0.33% TINUVIN 328 19.3 25.0 0.67% TINUVIN
144 *All formulations in Table 3 contain 0.33% IRGANOX .RTM. 1010
and 0.17% IRGAFOS .RTM. 126
* * * * *