Title of Invention

STABILIZER COMPOSITION FOR POLYMERS

Abstract The invention relates to stabilized thermoplastic polymers, in particular poiyolefin films. The stabilizing composition contains a tertiary amine with a molecular weight greater than 400 g/mol, a UV-absorber and/or a sterically hindered amine light stabilizer (HALS). Further aspects of the invention are a process for stabilizing thermoplastic polymers and the use of the above composition for stabilizing thermoplastic polymers.
Full Text

stabilizer Composition for Polymers
The invention relates to stabilized thermoplastic polymers, in particular polyolefin films. The stabilizing composition contains a tertiary amine with a molecular weight greater than 400 g/mol, a UV-absorber and/or a sterically hindered amine light stabilizer (HALS). Further aspects of the invention are a process for stabilizing thermoplastic polymers and the use of the above composition for stabilizing thermoplastic polymers.
Tertiary amines, in particular bridged amine compounds, such as diazabicyclooctane (DABCO) and triazadamantane derivatives in combination with sterically hindered amines are disclosed in WO 00/09604 and in WO 98/36023. The tertiary amines described therein are all of low molecular weight, which leads to problems during processing of the polymers due to their volatility and high migration rate.
It has now been found that the incorporation of aliphatic tertiary amines, which need not to be bridged, leads to a strong synergistic effect with UV-absorbers and/or sterically hindered amine light stabilizers (HALS). The synergistic effects are amplified when the polymers are exposed to a sulphur-based pesticide treatment, a common practice in greenhouse applications. Under such conditions the stability of polymers containing tertiary amines and UV-absorbers is particularly good.
The combination of UV-absorbers, tertiary amines and HALS provides in many cases the best stabilization.
Additionally, the photostability of UV-absorbers is increased. In particular hydroxyphenyl triazine UV-absorbers are relatively susceptible to the interaction with pesticides, especially towards sulphur-based pesticides. The use of a small amount of an aliphatic tertiary amine with high molecular weight increases their durability, that is, their persistency in the polymer articles.
This is particularly important for films used as greenhouse covers or for mulching. These structures are usually made of low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ethylvinylacetate (EVA) or ethylene/butylacrylate (EBA) and contain several additives with a functional effect: antioxidants, such as phenols, phosphates, lactones or hydroxylamines, slip agents and anti-blocking additives, such as erucamide,

oleamide or silica, mineral fillers, such as l Beside films, raffia, for example made of HOPE, PP, LDPE is frequently used with the same purposes in greenhouse or mulching applications.
The films and raffia are frequently exposed to the chemicals utilized as pesticides, herbicides and soil disinfectants used to protect crops and flowers. Very often, such compounds are based on chlorine, sulphur and metals (Cu, Fe). All these species are able to react with the stabilizers, leading to premature degradation of the film. Sulphur is known to be very effective, both as elemental powder sublimated or sprayed in the greenhouses and as part of active molecules (e.g. Vapam).
Beside the interaction with the stabilizers, sulphur is suspected to interact directly with the polyolefinic matrix, accelerating its degradation.
Finally, sulphur and sulphur-based compounds can interact with hydroxyphenil-triazines, leading not only to premature degradation but also to the loss of the UV-filter effect, used to improve productivity of the crops.
Some types of crops are in fact degraded by the UV-components of solar radiation, which must be filtered off to obtain high quality and yields. Additionally, some micro-organisms, e.g. Botrytis Cinerea, can proliferate under specific UV-irradiation. These pests are harmful for the cultivation of some varieties of roses [R. Reuven et al.. Development of photoselective PE films for control of foliar pathogens in greenhouse-grown crops, Plasticulture No. 102, pg. 7 (1994); Y. Eheshel et al., "The use of UV absorbing plastic sheets to protect crops against insects and spread of virus diseases", CIPA Congress 1997].
PP or PE tapes used as artificial grass are another application that combines a high exposure to UV-light (with the subsequent need for stabilization) with contamination of sulphur, used as vulcanizer for the rubber that represents the bottom of the artificial grass. The stability of such systems can be further affected by the presence of pigments that can act as pro-degradants.

One aspect of the invention is a stabilized polymer composition comprising
a) a thermoplastic polymer;
b) a tertiary amine with a molecular weight greater than 400 g/mol, which is not a 2,2,6,6 tetramethylpiperidine derivative;
c1) a UV-absorber selected from the group consisting of the hydroxyphenyl benzotriazoles,
hydroxyphenyl triazines, hydroxy benzophenones and oxalic anilides; or
c2) a light stabilizer from the class of sterically hindered amines; or
c3) a mixture of the UV-absorber, component c1) and the sterically hindered amine,
component c2).
In particular one aspect of the invention is a stabilized polymer composition comprising
a) a non halogen containing thermoplastic polymer;
b) an aliphatic tertiary amine with a molecular weight greater than 400 g/mol, which is not a 2,2,6,6 tetramethylpiperidine derivative;
c1) a UV-absorber selected from the group consisting of the hydroxyphenyl benzotriazoles,
hydroxyphenyl triazines, hydroxy benzophenones and oxalic anilides; or
c2) a light stabilizer from the class of sterically hindered amines; or
c3) a mixture of the UV-absorber, component c1) and the sterically hindered amine,
component c2).
Preferably the tertiary amine has a molecular weight of more than 500 g/mol, in particular of more than 700 g/mol.
In some cases it may be sufficient that the composition comprises a tertiary amine and a UV-absorber, as defined above. However, when maximum stabilization is required, the composition comprises a tertiary amine, a UV-absorber and a sterically hindered amine.
Examples of thermoplastic polymers are given below.
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, po-lybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HOPE), 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).
Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, prefe¬rably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
a) radical polymerisation (normally under high pressure and at elevated temperature).
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 n- or a-coordinated. These
metal complexes may be in the free form or fixed on substrates, typically on
activated magnesium chloride, titanium(lll) 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 la, lla and/or Ilia 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).
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).
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 copo¬lymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene

copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycioolefin 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/vi-nylcyclohexene copolymers, ethylene/alkyi acrylate copolymers, ethylene/alkyi 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/ethy-lene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyal-kylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.
4. Hydrocarbon resins (for example C5-C9) including hydrogenated modifications thereof
(e.g. tackifiers) and mixtures of polyalkylenes and starch.
Homopolymers and copolymers from 1.) - 4.) may have any stereostructure including syndio-tactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
5. Polystyrene, poly(p-methylstyrene), poly(a-methylstyrene).
6. Aromatic homopolymers and copolymers derived from vinyl aromatic monomers including styrene, a-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. Ste¬reoblock polymers are also included.
6a. Copolymers including aforementioned vinyl aromatic monomers and comonomers selec¬ted from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene/bu-tadiene, styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkyi methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyi methacrylate, styrene/maleic anhy-

dride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copo¬lymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/pro-pylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/sty-rene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propy-lene/styrene.
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).
6c. Hydrogenated aromatic polymers derived from hydrogenation of polymers mentioned under 6a.).
Homopolymers and copolymers may have any stereostructure including syndiotactic, isotac-tic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.
7. Graft copolymers of vinyl aromatic monomers such as styrene or a-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acry-lonitrile copolymers; styrene and acryionitrile (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 polyalkyi acrylates or polyalkyi 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.
8. Polymers derived from a,p-unsaturated acids and derivatives thereof such as polyacry-lates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacryloni-triles, impact-modified with butyl acrylate.
9. Copolymers of the monomers mentioned under 8) with each other or with other unsatu¬rated monomers, for example acrylonitrile/ butadiene copolymers, acrylonitrile/alkyi acrylate

copolymers, acrylonitrile/alkoxyalkyi acrylate or acrylonitrile/vinyl halide copolymers or acry-lonitrile/ alkyl methacrylate/butadiene terpolymers.
10. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or ace-tals 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.
11. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethy¬lene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
12. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain
ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes,
acrylates or MBS.
13. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.
14. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadi-enes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.
15. 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 ela¬stomer 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).

16. Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins
and polybenzimidazoles.
17. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids
or the corresponding lactones, for example polyethylene terephthalate, polybutylene tereph-
thalate, 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.
18. Polycarbonates and polyester carbonates.
19. Polyketones.
20. Polysulfones, polyether sulfones and polyether ketones.
21. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Poly-
amide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA,
PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR,
POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP,
PA/PPO, PBT/PC/ABS or PBT/PET/PC.
Preferably the thermoplastic polymer is low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polypropylene (PP) or ethylvinylacetate (EVA).
In a specific embodiment the composition is in the form of a film or tape.
For example the hydroxybenzophenone is of formula I

the 2-hydroxyphenylbenzotriazole is of formula lla, lib or He



having 1 to 12 carbon atoms;
in the compounds of the formula (Ha),
Ri Is hydrogen, alkyl having 1 to 24 carbon atoms, phenylalkyi having 1 to 4 carbon atoms In
the alkyl moiety, cycloalkyi having 5 to 8 carbon atoms or a radical of the formula

R4 and R5 Independently of one another are alkyl having in each case 1 to 5 carbon atoms,
or R4, together with the radical CnHan+i-m, forms a cycloalkyi radical having 5 to 12 carbon
atoms,
m is 1 or 2, n is an integer from 2 to 20 and
M is a radical of the formula -COORe in which
Re is hydrogen, alkyl having 1 to 12 carbon atoms, alkoxyalkyl having In each case 1 to 20
carbon atoms in the alkyl moiety and in the alkoxy moiety or phenylalkyi having 1 to 4 carbon
atoms in the alkyl moiety,
R2 is hydrogen, halogen, alkyl having 1 to 18 carbon atoms, and phenylalkyi having 1 to 4
carbon atoms in the alkyl moiety, and
R3 is hydrogen, chlorine, alkyl or alkoxy having in each case 1 to 4 carbon atoms or -COORe
in which Re is as defined above, at least one of the radicals Ri and R2 being other than
hydrogen;
in the compounds of the formula (lib)
T is hydrogen or alkyl having 1 to 6 carbon atoms,
Ti is hydrogen, chlorine or alkyl or alkoxy having in each case 1 to 4 carbon atoms,
n is 1 or 2 and,
if n is 1,


T3 is hydrogen, alkyl which has 1 to 18 carbon atoms and is unsubstituted or substituted by 1 to 3 hydroxyl groups or by -OCOTe, alkyl which has 3 to 18 carbon atoms, is interrupted once or several times by -O- or -NTs- and is unsubstituted or substituted by hydroxyl or -OCOTs, cycloalkyi which has 5 to 12 carbon atoms and is unsubstituted or substituted by hydroxyl and/or alkyl having 1 to 4 carbon atoms, alkenyl which has 2 to 18 carbon atoms and is unsubstituted or substituted by hydroxyl, phenylalkyi having 1 to 4 carbon atoms in the alkyl

T4 and T5 independently of one another are hydrogen, alkyl having 1 to 18 carbon atoms,
alkyl which has 3 to 18 carbon atoms and is interrupted once or several times by -O- or
-NTg-, cycloalkyi having 5 to 12 carbon atoms, phenyl, phenyl which is substituted by alkyl
having 1 to 4 carbon atoms, alkenyl having 3 to 8 carbon atoms, phenylalkyi having 1 to 4
carbon atoms in the alkyl moiety or hydroxyalkyi having 2 to 4 carbon atoms,
Te is hydrogen, alkyl having 1 to 18 carbon atoms, cycloalkyi having 5 to 12 carbon atoms,
alkenyl having 3 to 8 carbon atoms, phenyl, phenyl which is substituted by alkyl having 1 to 4
carbon atoms, phenylalkyi having 1 to 4 carbon atoms in the alkyl moiety,
T7 is hydrogen, alkyl having 1 to 18 carbon atoms, phenyl which is unsubstituted or
substituted by hydroxyl, phenylalkyi having 1 to 4 carbon atoms in the alkyl moiety, or -
CH2OT8,
Te is alkyl having 1 to 18 carbon atoms, alkenyl having 3 to 8 carbon atoms, cycloalkyi having
5 to 10 carbon atoms, phenyl, phenyl which is substituted by alkyl having 1 to 4 carbon
atoms, or phenylalkyi having 1 to 4 carbon atoms in the alkyl moiety,
Tg is alkylene having 2 to 8 carbon atoms, alkenylene having 4 to 8 carbon atoms, alkynylene
having 4 carbon atoms, cyclohexylene, alkylene which has 2 to 8 carbon atoms and is
interrupted once or several times by -0-, or a radical of the formula -
CH2CH(OH)CH20TiiOCH2CH(OH)CH2- or -CH2-C(CH20H)2-CH2-,
T10 is alkylene which has 2 to 20 carbon atoms and can be interrupted once or several times
by -0-, or cyclohexylene,
T11 is alkylene having 2 to 8 carbon atoms, alkylene which has 2 to 18 carbon atoms and is
interrupted once or several times by -0-, 1,3-cyclohexylene, 1,4-cyclohexylene, 1,3-
phenylene or 1,4-phenylene, or
T10 and Te, together with the two nitrogen atoms, are a piperazine ring;

in the compounds of formula (He)
R'2 is CrCi2alkyl and l in the compounds of the formula (III)
u is 1 or 2 and r is an integer from 1 to 3, the substituents
Yi independently of one another are hydrogen, hydroxyl, phenyl or halogen, halogenomethyl,
alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 18 carbon atoms, alkoxy having 1 to 18
carbon atoms which is substituted by a group -C00(Ci-Ci8alkyl);
if u is 1,
Y2 is alkyl having 1 to 18 carbon atoms, phenyl which is unsubstituted or substituted by
hydroxyl, halogen, alkyl or alkoxy having 1 to 18 carbon atoms;
alkyl which has 1 to 12 carbon atoms and is substituted by -COOH, -COOYs, -CONH2, -
CONHY9, -CONY9Y10, -NH2, -NHYg, -NY9Y10, -NHCOY11, -CN and/or -OCOYn;
alkyl which has 4 to 20 carbon atoms, is interrupted by one or more oxygen atoms and is
unsubstituted or substituted by hydroxyl or alkoxy having 1 to 12 carbon atoms, alkenyl
having 3 to 6 carbon atoms, glycidyl, cyclohexyl which is unsubstituted or substituted by
hydroxyl, alkyl having 1 to 4 carbon atoms and/or -OCOYn, phenylalkyi which has 1 to 5
carbon atoms in the alkyl moiety and is unsubstituted or substituted by hydroxyl, chlorine
and/or methyl, -COY12 or -SO2Y13, or,
if u is 2,
Y2 is alkylene having 2 to 16 carbon atoms, alkenylene having 4 to 12 carbon atoms,
xylylene, alkylene which has 3 to 20 carbon atoms, is interrupted by one or more -O- atoms
and/or is substituted by hydroxyl, -CH2CH(OH)CH2-0-Yi5-OCH2CH(OH)CH2, -CO-Y16-CO-, -
CO-NH-Y17-NH-CO- or -(CH2)m-C02-Yi8-OCO-(CH2)m, in which
m is 1, 2 or 3,
Ys is alkyl having 1 to 18 carbon atoms, alkenyl having 3 to 18 carbon atoms, alkyl which has
3 to 20 carbon atoms, is interrupted by one or more oxygen or sulfur atoms or -NTe- and/or is
substituted by hydroxyl, alkyl which has 1 to 4 carbon atoms and is substituted by -
P(0)(OYi4)2, -NY9Y10 or -OCOY11 and/or hydroxyl, alkenyl having 3 to 18 carbon atoms,
glycidyl, or phenylalkyi having 1 to 5 carbon atoms in the alkyl moiety,
Yg and Y10 independently of one another are alkyl having 1 to 12 carbon atoms, alkoxyalkyl
having 3 to 12 carbon atoms, dialkylaminoalkyi having 4 to 16 carbon atoms or cyclohexyl
having 5 to 12 carbon atoms, or Yg and Y10 together are alkylene, oxaalkylene or azaalkylene
having in each case 3 to 9 carbon atoms.

Yii is alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 18 carbon atoms or phenyl,
Yi2 is alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 18 carbon atoms, phenyl, alkoxy
having 1 to 12 carbon atoms, phenoxy, alkylamino having 1 to 12 carbon atoms or
phenylamino,
Yi3 is alkyl having 1 to 18 carbon atoms, phenyl or alkylphenyl having 1 to 8 carbon atoms in
the alkyl radical,
Yi4 is alkyl having 1 to 12 carbon atoms or phenyl,
Yi5 is alkylene having 2 to 10 carbon atoms, phenylene or a group -phenylene-M-phenylene-
in which M is -0-, -S-, -SO2-, -CH2- or -C(CH3)2-,
Y16 is alkylene, oxaalkylene or thiaalkylene having in each case 2 to 10 carbon atoms,
phenylene or alkenylene having 2 to 6 carbon atoms,
Yi7 is alkylene having 2 to 10 carbon atoms, phenylene or alkylphenylene having 1 to 11
carbon atoms in the alkyl moiety, and
Y18 is alkylene having 2 to 10 carbon atoms or alkylene which has 4 to 20 carbon atoms and
is interrupted once or several times by oxygen;
in the compounds of the formula (IV) x is an integer from 1 to 3 and the substituents L
independently of one another are hydrogen, alkyl, alkoxy or alkylthio having in each case 1 to
22 carbon atoms, phenoxy or phenyithio.
Ci-CiBalkyl may be linear or branched. Examples of alkyl having up to 18 carbon atoms 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-ethylhexyl, 1,1,3-trimethyl-hexyl, 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.
In the compounds of the formula (Ha) Ri can be hydrogen or alkyl having 1 to 24 carbon atoms, such as methyl, ethyl, propyl, butyl, hexyl, octyl, nonyl, dodecyl, tetradecyl, hexadecyl, octadecyl, nonadecyl and eicosyl and also corresponding branched isomers. Furthermore, in addition to phenylalkyi having 1 to 4 carbon atoms in the alkyl moiety, for example benzyl, Ri can also be cycloalkyi having 5 to 8 carbon atoms, for example
R4 cyclopentyl, cyclohexyl and cyclooctyi, or a radical of the formula —1 CnHjp+i ^-M^ in
^^ n n -m

which R4 and R5 independently of one another are alkyl having in each case 1 to 5 carbon atoms, in particular methyl, or R4, together with the CnH2n+i-m radical, forms a cycloalkyi radical having 5 to 12 carbon atoms, for example cyclohexyl, cyclooctyl and cyclodecyl. M is a radical of the formula -COORe in which Re is not only hydrogen but also alkyl having 1 to 12 carbon atoms or alkoxyalkyl having 1 to 20 carbon atoms in each of the alkyl and alkoxy moieties. Suitable alkyl radicals Re are those enumerated for Ri. Examples of suitable alkoxyalkyl groups are -C2H4OC2H5, -C2H4OC8H17 and -C4H8OC4H9. As phenylalkyi having 1 to 4 carbon atoms, Re is, for example, benzyl, cumyl, a-methylbenzyl or phenylbutyl.
In addition to hydrogen and halogen, for example chlorine and bromine, R2 can also be alkyl having 1 to 18 carbon atoms. Examples of such alkyl radicals are indicated in the definitions of Ri. R2 can also be phenylalkyi having 1 to 4 carbon atoms in the alkyl moiety, for example benzyl, a-methylbenzyl and cumyl.
Halogen as a substituent means In all cases fluorine, chlorine, bromine or iodine, preferably chlorine or bromine and more preferably chlorine.
At least one of the radicals Ri and R2 must be other than hydrogen.
In addition to hydrogen or chlorine, R3 is also alkyl or alkoxy having in each case 1 to 4 carbon atoms, for example methyl, butyl, methoxy and ethoxy, and also -COORe.
In the compounds of the formula (Mb) T is hydrogen or alkyl having 1 to 6 carbon atoms, such as methyl and butyl, J^ is not only hydrogen or chlorine, but also alkyl or alkoxy having in each case 1 to 4 carbon atoms, for example methyl, methoxy and butoxy, and, if n is 1, T2 is chlorine or a radical of the formula -OT3 or -NT4T5. T3 is here hydrogen or alkyl having 1 to 18 carbon atoms (cf. the definition of Ri). These alkyl radicals can be substituted by 1 to 3 hydroxy! groups or by a radical -OCOTe. Furthermore, T3 can be alkyl having 3 to 18 carbon atoms (cf. the definition of Ri) which is interrupted once or several times by -O- or -NTe- and is unsubstituted or substituted by hydroxyl or -OCOTe. Examples of T3 as cycloalkyi are cyclopentyl, cyclohexyl or cyclooctyl. T3 can also be alkenyl having 2 to 18 carbon atoms. Suitable alkenyl radicals are derived from the alkyl radicals enumerated in the definitions of Ri. These alkenyl radicals can be substituted by hydroxyl. Examples of T3 as phenylalkyi are benzyl, phenylethyl, cumyl, a-methylbenzyl or benzyl. T3 can also be a radical of the formula


Like T3, T4 and T5 can, independently of one another, be not only hydrogen but also alkyl having 1 to 18 carbon atoms or alkyl which has 3 to 18 carbon atoms and is interrupted once or several times by -O- or -NTs-. T4 and T5 can also be cycloalkyi having 5 to 12 carbon atoms, for example cyclopentyl, cyclohexyl and cyclooctyl. Examples of T4 and T5 as alkenyl groups can be found in the illustrations of T3. Examples of T4 and T5 as phenylalkyi having 1 to 4 carbon atoms in the alkyl moiety are benzyl or phenylbutyl. Finally, these substituents can also be hydroxyalkyi having 1 to 3 carbon atoms.

In addition to hydrogen, Te (see above also) is alkyl, cycloalkyi, alkenyl, aryl or phenylalkyi; examples of such radicals have already been given above.
In addition to hydrogen and the phenylalkyi radicals and long-chain alkyl radicals mentioned above, T7 can be phenyl or hydroxyphenyl and also -CH2OT8 in which Ts can be one of the alkyl, alkenyl, cycloalkyi, aryl or phenylalkyi radicals enumerated.
The divalent radical Tg can be alkylene having 2 to 8 carbon atoms, and such radicals can also be branched. This also applies to the alkenylene and alkynylene radicals Tg. As well as cyclohexylene, Tg can also be a radical of the formula CH2CH(OH)CH20TiiOCH2CH(OH)CH2- or -CH2-C(CH20H)2-CH2-.
T10 is a divalent radical and, in addition to cyclohexylene, is also alkylene which has 2 to 20 carbon atoms and which can be interrupted once or several times by -0-. Suitable alkylene radicals are derived from the alkyl radicals mentioned in the definitions of Ri.
T11 is also an alkylene radical. It contains 2 to 8 carbon atoms or, if it is interrupted once or several times by-0-, 4 to 10 carbon atoms. Tn is also 1,3-cyclohexylene, 1,4-cyclohexylene,

1,3-phenylene or 1,4-phenylene.
Together with the two nitrogen atoms, Te and Tio can also be a piperazine ring.
Examples of alkyl, alkoxy, phenylalkyi, alkylene, alkenylene, alkoxyalkyl and cycloalkyi radicals and also alkylthio, oxaalkylene or azoalkylene radicals in the compounds of the formulae (I), (lla), (lib), (lie), (III) and IV) can be deduced from the above statements.
Within the benzotriazole UV-absorbers those according to formula lla are in general preferred.
The UV absorbers of the formulae (I), (lla), (lib), (He), (III) and (IV) are known per se and are described, together with their preparation in, for example, WO 96/28431, EP-A-323 408, EP-A-57 160, US 5 736 597 (EP-A-434 608), US 4 619 956, DE-A 31 35 810 and GB-A 1 336 391. Preferred meanings of substituents and individual compounds can be deduced from the documents mentioned.
In another embodiment the UV-absorber of the class of hydroxyphenyl triazines is of formula (IV)

in which n is 1 or 2;
R^, R'^, Rj and R'^, independently of one another, are H, OH, C^-C^j^lkyl; C2-Cgalkenyl; C^-
C^^a'koxy; C^-C^galkenoxy; halogen; trifluoromethyl; C^-C^^phenylalkyi; phenyl; phenyl which

is substituted by C^-C^galkyl, C^-C^galkoxy or halogen; phenoxy; or phenoxy which is
substituted by C^-C^gakyl, C^-C^gall R3 and R^, independently of one another, are H, C^-C^^^lkyl; OR'^; C^-CgBlkenyl; C^-
C^galkenoxy; halogen; trifluoromethyl; C^-C^^phenylalkyl; phenyl; phenyl which is substituted
by C^-C^galkyl, C^-C^galkoxy or halogen; phenoxy; or phenoxy which is substituted by C^-
C^galkyl, C^-C^galkoxy or halogen;
Rg is hydrogen, C^-Cg^alkyl, Cg-C^^^y^loalkyl or C^-C^gphenylalkyl;
R^, in the case where n = 1, and R'^, independently of one another, are hydrogen or C^-
C^galkyl; or are C^-C^^^lkyl which is substituted by OH, C^-C^galkoxy, allyloxy, halogen, -
COOH, -COORg, -CONH^, -CONHRg. -CON(Rg)(R^„), -NH^, -NHRg, -N(Rg)(R^^), -NHCOR^^, -
CN, -OCOR^^, phenoxy and/or phenoxy which is substituted by C^-C^galkyl, C^-C^galkoxy or
halogen; or R^ is Cg-CggalkyI which is interrupted by -O- and may be substituted by OH; or R^
is Cg-Cgalkenyl; glycidyl; Cg-C^^^y^'o^lkyl; cyclohexyl which is substituted by OH, C^-C^alkyl
or -OCOR^^; C^-C^^phenylalkyl which is unsubstituted or substituted by OH, CI or CH3; -00-
R12 or -so^-R,3;
R^, in the case where n = 2, is C^-C^galkylene, C^-C^^^'kenylene, xylylene, Cg-CjQalkylene which is interrupted by O and/or substituted by OH, or is a group of the formula -CH2CH(OH)CH20-R2(,-OCH2CH(OH)CH2-, -CO-R^^-CO-, -CO-NH-R^^-NH-CO- or -(CH^)^-COO-R,-OOC-(CH,) -, in which m is a number in the range from 1 to 3, or is
23 ^ 2'm

Rg is C^-C^ga!kyl; C^-C^galkenyl; hydroxyethyl; Cg-Cggalkyl which is interrupted by O, NH, NRg
or S and/or is substituted by OH; C^-C^alkyl which is substituted by -P(0)(OR^4)2, -N(Rg)(R^Q)
or -OCOR^^ and/or OH; glycidyl; C5-C^2cycloalkyl; phenyl; C^-C^^alkylphenyl or C^-
C^^phenylalkyl;
Rg and R^^, independently of one another, are C^-C^^^lkyl; C3-C^23lkoxyalkyl; C^-
C^gdlalkylaminoalkyl or Cg-C^2cyc'°3"^y' O"" ^^9 ^'^^ ^^o together are Cg-Cgalkylene or -
oxaalkylene or -azaalkylene;
R^^ is C^-C^galkyl; C2-C^galkenyl or phenyl; C^-C^^hydroxyalkyl; cyclohexyl; or is Cg-CggalkyI
which is interrupted by -O- and may be substituted by OH;
R^2 is C^-C^galkyl; C^-C^galkenyl; phenyl; C^-C^galkoxy; Cg-C^galkenyloxy; Cg-Cggalkoxy which
is interrupted by O, NH, NRg or S and/or substituted by OH; cyclohexyloxy; C^-

C^^alkylphenoxy; C^-C^^phenylalkoxy; phenoxy; C^-C^^^lkylamino; phenylamino; tolylamino
or naphthylamino;
R^3 is C^-C^j^'M; phenyl; naphthyl or C^-C^^alkylphenyl;
R^^ is C^-C^2^lkyl, methylphenyl or phenyl;
^20 '® Cj-C^galkylene; C^-Cg^alkylene which is Interrupted by O, phenylene or a -phenylene-
X-phenylene- group, in which X is -0-, -S-, -SO^-, -CH^- or -CCCHg)^-;
R^^ is Cg-C^^alkylene, C^-C^gOxaalkylene, C^-C^^thiaalkylene, Cg-C^^^ryiene or C^-
Cgalkenylene;
R22 is Cg-C^^alkylene, phenylene, tolylene, diphenylenemethane or a
group; and
R23 is C2-C^galkylene or C^-C2Qalkylene which Is interrupted by O.
Halogen is in all cases fluorine, chlorine, bromine or iodine.
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.
Examples of alkoxy having up to 12 carbon atoms are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy.
Examples of alkenoxy are propenyloxy, butenyloxy, pentenyloxy and hexenyloxy.
Examples of C5-Ci2cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclo-dodecyl. Cs-CeCycioalkyJ, especially cyclohexyl, is preferred.
Ci-C4Alkyl-substituted Cs-CiacycloalkyI is for example methylcyclohexyl or dimethyl-cyclohexyl.

OH- and/or CrCioalkyl-substituted phenyl is for example methylphenyl, dimethylphenyl, trlmethylphenyl, tert-butylphenyl or 3,5-dl-tert-butyl-4-hydroxypheny!.
Alkoxy-substituted phenyl is for example methoxyphenyl dimethoxyphenyl or trimethoxy-phenyl.
Examples of C7-C9phenylalkyl are benzyl and phenylethyl.
Cr-CgPhenylalkyI which is substituted on the phenyl radical by -OH and/or by alkyl having up to 10 carbon atoms is for example methylbenzyl, dimethylbenzyl, trimethylbenzyl, tert-butylbenzyl or 3,5-di-tert-butyl-4-hydroxybenzyl.
Examples of alkenyl are allyl, 2-methallyl, butenyl, pentenyl and hexenyl. Allyl is preferred. The carbon atom in position 1 is preferably saturated.
Examples of alkylene are methylene, ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octa-methylene and decamethylene.
Example s of alkenylene are butenylene, pentenylene and hexenylene.
C6-C12 arylene is preferably phenylene.
Alkyl interrupted by O is for example -CH2-CH2-O-CH2-CH3, -CH2-CH2-O-CH3- or -CH2-CH2-O-CH2-CH2-CH2-O-CH2-CH3-. It is preferably derived from polyethlene glycol. A general description is -((CH2)a-0)b-H/CH3, wherein a is a number from 1 to 6 and b is a number from 2 to 10.
C2-C10 oxaalkylene and C2-Ciothiaalkylene can be deduced from the above mentioned alkylene groups by substituting one or more carbon atoms by an oxygen atom or a sulphur atom.
For instance the hydroxyphenyl triazine UV-absorbers are 2-(2-hydroxyphenyl)-1,3,5-triazines are for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-

4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-
bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-
dimethylphenyl)-1,3,5-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-triazine, 2-(2-
hydroxy-4-trldecyloxyplienyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-
hydroxy-3-butyloxy-propoxy)phenyl]-4,6-bis(2,4-dinnethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-
hydroxy-3-octyloxy-propyloxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-
(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-dimetliyl-plienyl)-1,3,5-triazine, 2-(2-liydroxy-4-liexyloxy)plienyl-4,6-diphenyl-1,3,5-triazine, 2-(2-hy-droxy-4-methoxyphenyl)-4,6-diplienyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-liy-droxy-propoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-plienyl-1,3,5-triazine, 2-{2-liydroxy-4-[3-(2-ethylliexyl-1-oxy)-2-liydroxypropyloxy]plienyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-(2-hydroxy-4-(2-ethyiliexyl)oxy)phenyl-4,6-di(4-plienyl)phenyl-1,3,5-triazine.
Specific liydroxyphenyl triazine UV-absorbers are, for example, tliose according to following formulae:









The hydroxyphenyl triazine UV-absorbers are known and partially items of commerce. They are for example disclosed in WO 96/28431.
Specific examples of 2-hydroxybenzophenones are for example the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
Specific examples of 2-(2'-hydroxyphenyl)benzotriazoles are 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)ben-zotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl- 2'-hydroxy-5'-methylphenyl)-5-chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl-2'-hydroxyphe-nyl)benzotriazole, 2-(2'-hydroxy-4'-octyloxyphenyl)benzotriazole, 2-(3',5'-di-tert-amyl-2'-hy-droxypheny!)benzotriazole, 2-(3',5'-bis-(a,a-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)-5-chioro-benzotriazole, 2-(3'-

tert-butyl-5'-[2-(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hyclroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)car-bonylethyl]-2'-hydroxyphenyI)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzo-triazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol]; the transesterification product of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole
with polyethylene glycol 300; [R-CH2CH2—COO-CHjCHj-}- where R = 3'-tert-butyl-4'-
hydroxy-5'-2H-benzotriazol-2-ylphenyl, 2-[2'-hydroxy-3'-(a,a-dimethylbenzyl)-5'-(1,1,3,3-tetra-methylbutyl)-phenyl]benzotriazole; 2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(a,a-dinne-thylbenzyl)-phenyl]benzotriazole.
Specific examples for oxamides are for example 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanllide, 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 0- and p-methoxy-disubstituted oxanilides and mixtures of 0- and p-ethoxy-disubstituted oxanilides.
The above mentioned UV-absorbers are largely items of commerce and for example known as Tinuvin® 109, 171, 326, 327, 328, 350, 360, 384, 400, 405, 411 or Chimassorb® 81 from Ciba Specialty Chemicals or Cyasorb® 1164 from Cytech Inc.
In many cases it may be of advantage to use a combination of UV-absorbers from different classes, such as for example a benzophenone UV-absorber with a benzotriazole UV-absorber or a hydroxyphenyltriazine UV-absorber with a benzotriazole UV-absorber. If such a combination is used, the weight ratio between both UV-absorbers is for example from 1:5 to 5:1, for instance from 1:3 to 3:1, particularly 1:1.5 to 1.5:1.
For example the sterically hindered amines are selected from the group consisting of
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-plperidyl)hexamethylenedlamine 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-
plperidyl)-1,2,3,4-butanetetracarboxylate, 1,1'-(1 -2-ethanediyl)-bis(3,3,5,5-tetrame-
thylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethyl-piperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)-malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, bis(1-octyl-oxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succi-nate, linear or cyclic condensates of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylene-diamine and 4-nnorpholino-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-triazine and 1,2-bis(3-anninopropylamino)-ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetranne-thyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidy!)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-tri-chloro-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-di-aza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene, N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetrame-thyl-4-piperidyl)hexamethylenediamine, 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-pentamethyi-4-aminopiperidine and the compound of example 2 of US-6117995 .

The sterically hindered amine compounds are preferably selected from the group consisting of the following commercial products:
DASTIB 845 (RTM), TINUVIN 770 (RTM), TINUVIN 765 (RTM), TINUVIN 144 (RTM), TINUVIN 123 (RTM), TINUVIN 371 (RTM), TINUVIN 111 (RTM), TINUVIN 783 (RTM), TINUVIN 791 (RTM), MARK LA 52 (RTM), MARK LA 57 (RTM), MARK LA 62 (RTM), MARK LA 67 (RTM), HOSTAVIN N 20 (RTM), HOSTAVIN N 24 (RTM), SANDUVOR 3050 (RTM), DIACETAM 5 (RTM), SUMISORB TM 61 (RTM), UVINUL 4049 (RTM), SANDUVOR PR 31 (RTM), GOODRITE UV 3034 (RTM), GOODRITE UV 3150 (RTM), GOODRITE UV 3159 (RTM), GOODRITE 3110 X 128 (RTM), UVINUL 4050 H (RTM), CHIMASSORB 944 (RTM). CHIMASSORB 2020 (RTM), CYASORB UV 3346 (RTM), CYASORB UV 3529 (RTM), DASTIB 1082 (RTM), CHIMASSORB 119 (RTM), UVASIL 299 (RTM), UVASIL 125 (RTM), UVASIL 2000 (RTM), UVINUL 5050 H (RTM), LICHTSCHUTZSTOFF UV 31 (RTM), LUCHEM HA B 18 (RTM), MARK LA 63 (RTM), MARK LA 68 (RTM), UVASORB HA 88 (RTM), TINUVIN 622 (RTM), HOSTAVIN N 30 (RTM) and FERRO AM 806 (RTM).
Particularly preferred are TINUVIN 770 (RTM). TINUVIN 371 (RTM), TINUVIN 791 (RTM), TINUVIN 622 (RTM), TINUVIN 783 (RTM), CHIMASSORB 944 (RTM), CHIMASSORB 2020 (RTM) and CHIMASSORB 119 (RTM).
For instance the tertiary amines are compounds of formulae (a) to Q)



wherein R301, R302 and R303 are independently Cio-Csealkyl;
R304, R305 and R306 are independently Cg-CsealkyI;
R310 and R311 are independently hydrogen or Ci-CisalkyI;
R307 and R308 are independently Ci-Csalkylene;
k is a number fronn
n is a number from 2 to 20;
m is a number from 4 to 20; and
X, y independently are numbers from 3 to 20.
Preferred are tertiary amines of formula (a).
The tertiary amines are largely items of commerce or can be prepared according to standard methods.
Typically the tertiary amine is present in an amount of 0.1-2%, preferably 0.2-1% by weight, based on the weight of the thermoplastic polymer.

For example, the UV-absorber is present in an amount of 0.01-2% preferably 0.2-2% by weight, based on the weight of the thermoplastic polymer.
For instance, the sterically hindered amine is present in an amount of 0.01-2%, preferably 0.1-1% by weight, based on the weight of the thermoplastic polymer.
Preferably the total amount of tertiary amine, UV-absorber and/or sterically hindered amine is from 0.2 to 4% by weight based on the weight of the thermoplastic polymer.
The stabilized material may additionally also contain various conventional additives, for
example:
1. Antioxidants
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-bu-tyl-4-isobutylphenol, 2,6-dlcyclopentyl-4-methylphenol, 2-(a-methylcyclohexyl)-4,6-dimethyl-phenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-meth-oxymethylphenol, 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-(r-methylheptadec-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltridec-1'-yl)phenol and mixtures there¬of.
1.2. Alkvlthiomethvlphenols. for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctyl-thiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.
1.3. Hydroouinones and alkylated hvdroquinones. for example 2,6-di-tert-butyl-4-methoxy-phenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octade-cyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-bu-tyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hy-droxyphenyl) adipate.
1.4. Tocopherols, for example a-tocophernl R-tnr.nnhfirnl v-toroDherol S-tocooherol and mixtures thereof (vitamin E).

1.5. Hvdroxvlated thiodiphenvl 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.
1.6. Alkvlidenebisphenols. for example 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebls(6-tert-butyl-4-ethylphenol), 2,2'-methylenebis[4-methyl-6-(a-methylcycIohexyl)-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-dl-tert-butyl-phenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis[6-(a-methylben-zyl)-4-nonylphenol], 2,2'-methylenebis[6-(a,a-dimethylbenzyl)-4-nonylphenol], 4,4'-methy-lenebls(2,6-dl-tert-butylphenol), 4,4'-methylenebis(6-tert-butyl-2-methylpheno!), 1,1 -bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bls(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 bls[3,3-bls(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopenta-diene, bls[2-(3'-tert-butyl-2'-hydroxy-5'-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephtha-late, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphe-nyl)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.
1.7. 0-. N- and S-benzvl compounds, for example 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydi-benzyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-dl-tert-butylbenzylmercaptoacetate, trls(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bls(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dlthioterephthaiate, bls(3,5-dl-tert-butyl-4-hydroxy-benzyl)sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
1.8. Hvdroxvbenzvlated malonates. for example dloctadecyl-2,2-bls(3,5-di-tert-butyi-2-hy-droxybenzyl)malonate, di-octadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, di-dodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, bis[4-( 1,1,3,3-te-tramethylbutyl)phenyl]-2,2-bis(3,5-dJ-tert-butyl-4-hydroxybenzyl)malonate.

1.9. Aromatic hvdroxvbenzyl compounds, for example 1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-
benzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetrame-
thylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
1.10. Triazine compounds, for example 2,4-bls(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxy-anilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-dl-tert-butyl-4-hydroxyanillno)-1,3,5-trl-azine, 2-octylmercapto-4,6-bis(3,5-dl-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazlne, 2,4,6-tris-(3,5-dl-tert-butyl-4-hydroxyphenoxy)-1,2,3-trlazine, 1,3,5-tris(3,5-dl-tert-butyl-4-hydroxyben-zyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate, 2,4,6-trls-(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-trlazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)-hexahydro-1,3,5-trJazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)Jso-cyanurate.
1.11. Benzvlphosphonates. for example dlmethyl-2,5-di-tert-butyl-4-hydroxybenzylphospho-nate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl3,5-di-tert-butyl-4-hy-droxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
1.12. Acvlaminophenols. for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-dl-tert-butyl-4-hydroxyphenyl)carbamate.
1.13. Esters of p-(3,5-di-tert-butvl-4-hvdroxvphenvnpropionic 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, diethy-lene glycol, triethylene glycol, pentaerythrltol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hy-droxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol-propane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.14. Esters of B-(5-tert-butvl-4-hvdroxv-3-methvlphenvl)propionic acid with mono- or poly¬hydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanedi¬ol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythrltol, tris(hydroxyethyl)isocyanurate, N,N'-bis-(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethyl-olpropane, 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-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]-undecane.
1.15. Esters of P-(3.5-dicvclohexvl-4-hvdroxvphenvl)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, tri-ethylene glycol, pentaerythritol, tris(hydroxyethy!)isocyanurate, N,N'-bis(hydroxyethyl)ox-amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy-droxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.16. Esters of 3.5-di-tert-butvl-4-hvdroxvphenvl acetic acid with mono- or polyhydric alco¬hols, 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, trls(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)ox-amide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hy-droxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.17. Amides of p-(3.5-di-tert-butvl-4-hvdroxvphenvl)propionic acid e.g. N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxy-phenylpropionyl)trimethylenediamide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hy-drazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Nau-gard®XL-1, supplied by Uniroyal).
1.18. Ascorbic acid (vitamin C)
1.19. Aminic antioxidants, for example N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-sec-bu-tyl-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'-dicy-clohexyl-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'-phe-nyl-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-isopropoxydiphenyl-amine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naph-

thylamine, octylated diphenylamine, for example p,p'-di-tert-octytdiphenylamine, 4-n-butyl-
aminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-
octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylamino-
methylphenol, 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(phenyl-
amino)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-octyldiphenyl-
amines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and
dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyl-
diphenylamines, 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, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetra-
methylpiperid-4-yl-hexamethylenediamine, bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate,
2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethy(piperidin-4-ol.
2. Metal deactivators, for example N,N'-diphenyloxamide, N-salicylal-N'-salicyloyI hydrazine, N,N'-bis(salicyloyl)hydrazine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyi dihydrazide, sebacoyi bisphenylhydrazide, N,N'-diacetyladipoyl dihydrazide, N,N'-bis(salicyl-oyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
3. Phosphites and phosphonites. for example triphenyl phosphite, diphenylaikyi phosphites, phenyldialkyi phosphites, tris(nonylphenyi) phosphite, trilauryl phosphite, trioctadecyi phos¬phite, 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-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, tristea-ryl 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-methyiphenyl)ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dlbenz[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'-te-




4. Hvdroxvlamines. 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-octadecylhydrox-
ylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine derived from
hydrogenated tallow amine.
5. 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-al-pha-heptadecylnitrone, N-ocatadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-hepta-decylnitrone, N-octadecyl-alpha-hexadecylnitrone, nitrone derived from N,N-dialkylhydroxyl-amine derived from hydrogenated tallow amine.
6. Thiosvnergists. for example dilauryl thiodipropionate or distearyl thiodipropionate.
7. Peroxide scavengers, for example esters of p-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercapto-benzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(p-dodecylmercapto)propionate.
8. 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.

9. 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(paramethyldibenzyli-
dene)sorbitol, and 1,3:2,4-di(benzylidene)sorbitol.
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.
11. Other additives, for example plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
12. Benzofuranones and indolinones. for example those disclosed in U.S. 4,325,863; U.S. 4,338,244; U.S. 5,175,312; U.S. 5,216,052; U.S. 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102 or 3-[4-(2-acetoxyethoxy)-phenyl]-5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]-benzofuran-2-one, 3,3'-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzo-furan-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2,3-dimethylphe-nyl)-5,7-di-tert-butylbenzofuran-2-one.
The above mentioned further stabilizers and additives are usually applied in an amount from 0.01% to 2%.
Also subject of the invention is a composition as described above which contains additionally a further stabilizer selected from the group consisting of a phenolic antioxidant, a phosphite or phosphonite and a benzofuranone or indolinone.

The above mentioned components and further additives can be incorporated into the thermoplastic polymer to be stabilized by known methods, for example before or during shaping or by applying the dissolved or dispersed compounds to the thermoplastic polymer, if necessary with subsequent evaporation of the solvent. The components can be added to the thermoplastic polymer in the form of a powder, granules or a masterbatch, which contains these components in, for example, a concentration of from 2.5 to 25% by weight.
If desired, the components can be melt blended with each other before incorporation in the thermoplastic polymer. They can also be added to the thermoplastic polymer before or during the polymerization.
The materials stabilized according to this invention can be used in a wide variety of forms, for example as films, fibres, tapes, moulding compositions or profiles.
Examples of processing or transformation of the thermoplastic polymer according to the present invention are:
Injection blow molding, extrusion, blow molding, rotomolding, in mold decoration (back injection), slush molding, injection molding, co-injection molding, forming, compression molding, pressing, film extrusion (cast film; blown film), fiber spinning (woven, non-woven), drawing (uniaxial, biaxial), annealing, deep drawing, calandering, mechanical transformation, sintering, coextrusion, coating, lamination, crosslinking (radiation, peroxide, silane), vapor deposition, weld together, glue, thermoforming, pipe extrusion, profile extrusion, sheet extrusion, extrusion coating, visbreaking (peroxide, thermal), fiber melt blown, spun bonded, surface treatment (corona discharge, flame, plasma), sterilization (by gamma rays, electron beams), cast polymerization (R&M process, RAM extrusion), gel-coating and tape extrusion.
The compositions are preferably in the form of films useful for packaging, dump, laminating, agriculture and horticulture, greenhouse, mulch, tunnel, silage, bale wrap, swimming pools, waste bags, wallpaper, stretch film, raffia, desalination film, batteries, and connectors.
Of particular interest are agriculture and horticulture applications, such as greenhouses, mulch, tunnels, shading nets, silage and raffia.

Further aspects of the invention are a method for the stabilization of a non halogen
containing thermoplastic polymer comprising incorporating into the thermoplastic polymer an
aliphatic tertiary amine with a molecular weight greater than 400 g/mol, which is not a 2,2,6,6
tetramethylpiperidine derivative;
a UV-absorber selected from the group consisting of the hydroxyphenyl benzotriazoles,
hydroxyphenyl triazines, hydroxy benzophenones and oxalic anilides; or
a light stabilizer from the class of sterically hindered amines; or a
a mixture of the UV-absorber and the sterically hindered amine;
and
the use of an aliphatic tertiary amine with a molecular weight greater than 400 g/mol, which is
not a 2,2,6,6 tetramethylpiperidine derivative; and
a UV-absorber selected from the group consisting of the hydroxyphenyl benzotriazoles,
hydroxyphenyl triazines, hydroxy benzophenones and oxalic anilides; or
a light stabilizer from the class of sterically hindered amines; or a
a mixture of the UV-absorber and the sterically hindered amine
for the stabilization of non halogen containing thermoplastic polymers.
Definitions and preferences have already been given; they apply also to the other aspects of the invention.
Polyethylenimines, which have secondary and tertiary amine groups, are also suitable in the sense of the instant invention. Examples for such polyethylenimines are given below.
The following examples illustrate the invention.
A Preparation Exxamples Example A1


15,1 g of polyethylenimine (Mw: 800) (0.35 mol of monomer) are dissolved in a 150 ml of iso propyl alcohol; 16,2 g (0.0878 mol) of dodecan aldheyde are dissolved in 50 ml of the same alcohol and are dropped to the previous solution, under Inert atmosphere: the reaction is exothermic. The mixture is warmed to boiling and 100 ml of solvent Is distilled off. After cooling to room temperature, the mixture is concentrated and 29.7 g of a yellow oil are recovered (y = 99%). ^H NMR 6 ppm 0.78 (t, 3H); 1 - 3.5 (m, 38,6 H)

15.4 g of polyethylenimine (Mw: 800) (0.36 mol of monomer) are dissolved in 200 ml of n-butyl alcohol; a solution of 29,7 g (0.22 mol) of potassium carbonate in 75 ml of water is added to the initial solution. The bi phase system is put under vigorous agitation under nitrogen. At the temperature of 85°C, 59,7 g (0.18 mol) of octadecyl bromide are slowly dropped to the system. After 2 hours under these conditions the mixture is cooled to room temperature and the aqueous layer is separated. The organic phase is concentrated. After the salts precipitate they are filtered off. The solution is concentrated and 58,3 g of yellow solid are obtained (y = 96%) ^H NMR 5 ppm 0.84 (t, 3H); 1.2 (s, 30.8 H); 2.0 -3.0 (m, 6.9 H)


40.0 g of octadecyl amine (0.15 mol) are dissolved in 250 ml of ethyl alcohol and 30 ml of water. The mixture is put under agitation and 5.3 g (0.18 mol) of p-formaldehyde are added, then the system is warmed to 75°C for 4 hours. After cooling to room temperature a solid precipitate is obtained, it is filtered and dried at 90'C. 40.7 g of wet solid (97%) are yielded. ^H NMR 6 ppm 0.86 (t, 3H); 1.0 - 1.5 (m, 29,6 H); 2.37 (t, 1.8 H); 3,3 (s, 1.8 H)

40.0 g of dodecane amine (0.22 mol) are dissolved in 200 ml of ethyl alcohol and 50 ml of water. The mixture is put under agitation and 7.8 g (0.26 mol) of p-formaldehyde are added, then the system is warmed to 75'C for 4 hours. The mixture is concentrated and 150 ml of solvent are distilled off, 200 ml of n hexane are added and the phases are separated. The hydrocarburic phase is concentrated and 42,5 g df a yellow oil is obtained (99%). 'H NMR 6 ppm 0.84 (t, 3H); 1.0-1.5 (m, 20.8 H); 2.37 (t, 2.0 H); 3.3 (s, 1.8 H)


10.0 g of polyethylenimine (Mw: 800) (0.23 mol of monomer) are dissolved in a 100 ml of iso propyl alcohol; 21.4 g (0.12 mol) of dodecane aldehyde are added to the previous solution, under inert atmosphere: the reaction is exothermic. The mixture is warmed to boiling and 70 ml of solvent is distilled off. After cooling to room temperature, the mixture is concentrated and 29.1 g of a yellow oil are recovered (99%). ^H NMR 6 ppm 0.80 (t, 3H); 1.2 (s, 19.5 H); 2.0 - 3.2 (m, 9.2 H)

20.0 g of N ethyl-di-ethanol amine (0.15 mol) are suspended in 20 ml of xylene and 21.9 g of di-methyl succinate are added. The mixture is heated to boiling temperature and some solvent is distilled off. After cooling 0.3 g of t-butylate of potassium are added as a catalyst, and the mixture is heated to 150°C under a current of nitrogen for 2,5 h, then the temperature is raised to ISO'C for 4 h. after cooling the mixture is diluted with toluene and washed with water, the organic phase is separated, dried and concentrated. 26.1 g of a brown oil are obtained (81%). ^H NMR 5 ppm 1.0 (t, 3H); 2.6 (s, 6.0 H); 2.7 (t, 4.0 H); 4.1 (t, 4.0 H)


20.0 g of polyethyleneimine and 10.1 g of methyl laurylate are put in a one neck flask of 50 ml and heated to at 185°C at atmospheric pressure for one hour. The pressure is reduced to 1mm Hg at the same temperature. After cooling to room temperature 28.4 g of a yellow oil is recovered (99%). 'HNMR5ppm 0.8 (t, 3H); 1.1 (s, 16.0 H); 1.5 (s, 11.3 H); 2.0-3.6 (m, 40.9 H)
B Application Examples Example B1
LDPE (Riblene FF29 from Polimeri Europe) blown extruded films are prepared and exposed in an Atlas Weather O Meter (WOM dry) and in a Q-UV weathering device. To simulate the environmental exposure to sulphur, each film was previously exposed to elemental sulphur vapour.
Before measuring the UVA degradation the films were washed with water in order to remove the sulphur. The degradation of UV absorber was monitored by UV-visible spectroscopy and calculated from the transmittance in the region 280-380 nm. The polymer matrix degradation was followed by carbonyl increment using FT-IR spectroscopy.
The results are presented in Tables 1-4.


Claims
1. A stabilized polymer composition comprising
a) a non Inalogen containing thermoplastic polymer;
b) an aliphatic tertiary amine with a molecular weight greater than 400 g/mol, which is not a 2,2,6,6 tetramethylpiperidine derivative;
c1) a UV-absorber selected from the group consisting of the hydroxyphenyl benzotriazoles,
hydroxyphenyl triazines, hydroxy benzophenones and oxalic anilides; or
c2) a light stabilizer from the class of sterically hindered amines; or
c3) a mixture of the UV-absorber, component c1) and the sterically hindered amine,
component c2).
2. A composition according to claim 1 wherein the thermoplastic polymer is low density
polyethylene (LDPE), linear low density polyethylene (LLDPE), polypropylene (PP) or
ethylvinylacetate (EVA).
3. A composition according to claim 1, which is in the form of a film or tape.
4. A composition according to claim 1 wherein the hydroxybenzophenone is of formula I



the compounds of the formula (I) v is an integer from 1 to 3 and w is 1 or 2 and the ibstituents Z independently of one another are hydrogen, halogen, hydroxyl or alkoxy jving 1 to 12 carbon atoms;
the compounds of the formula (Ma),
1 is hydrogen, alkyl having 1 to 24 carbon atoms, phenylalkyi having 1 to 4 carbon atoms in
e alkyl moiety, cycloalkyi having 5 to 8 carbon atoms or a radical of the formula


R4 and R5 independently of one another are alkyl having in each case 1 to 5 carbon atoms,
or R4, together with the radical CnH2n+i-r„, forms a cycloalky! radical having 5 to 12 carbon
atoms,
m is 1 or 2, n is an integer from 2 to 20 and
M is a radical of the formula -COORe in which
Re is hydrogen, alkyl having 1 to 12 carbon atoms, alkoxyalkyl having in each case 1 to 20
carbon atoms in the alkyl moiety and in the alkoxy moiety or phenylalkyi having 1 to 4 carbon
atoms in the alkyl moiety,
R2 is hydrogen, halogen, alkyl having 1 to 18 carbon atoms, and phenylalkyi having 1 to 4
carbon atoms in the alkyl moiety, and
R3 is hydrogen, chlorine, alkyl or alkoxy having in each case 1 to 4 carbon atoms or -COORe
in which Re is as defined above, at least one of the radicals Ri and R2 being other than
hydrogen;
in the compounds of the formula (lib)
T is hydrogen or alkyl having 1 to 6 carbon atoms,
Ti is hydrogen, chlorine or alkyl or alkoxy having in each case 1 to 4 carbon atoms,
n is 1 or 2 and,
if n is 1,

in which
T3 is hydrogen, alkyl which has 1 to 18 carbon atoms and is unsubstituted or substituted by 1 to 3 hydroxyl groups or by -OCOTe, alkyl which has 3 to 18 carbon atoms, is interrupted once or several times by -O- or -NTs- and is unsubstituted or substituted by hydroxyl or -OCOTe, cycloalkyi which has 5 to 12 carbon atoms and is unsubstituted or substituted by hydroxyl and/or alkyl having 1 to 4 carbon atoms, alkenyl which has 2 to 18 carbon atoms and is

unsubstituted or substituted by hydroxyl, phenylalkyi having 1 to 4 carbon atoms in the all T4and T5 independently of one another are hydrogen, alkyl having 1 to 18 carbon atoms,
alkyl which has 3 to 18 carbon atoms and is interrupted once or several times by -O- or
-NTe-, cycloalkyi having 5 to 12 carbon atoms, phenyl, phenyl which is substituted by alkyl
having 1 to 4 carbon atoms, alkenyl having 3 to 8 carbon atoms, phenylalkyi having 1 to 4
carbon atoms in the alkyl moiety or hydroxyalkyl having 2 to 4 carbon atoms,
Te is hydrogen, alkyl having 1 to 18 carbon atoms, cycloalkyi having 5 to 12 carbon atoms,
alkenyl having 3 to 8 carbon atoms, phenyl, phenyl which is substituted by alkyl having 1 to 4
carbon atoms, phenylalkyi having 1 to 4 carbon atoms in the alkyl moiety,
T7 is hydrogen, alkyl having 1 to 18 carbon atoms, phenyl which is unsubstituted or
substituted by hydroxyl, phenylalkyi having 1 to 4 carbon atoms in the alkyl moiety, or -
CH2OT8,
Te is alkyl having 1 to 18 carbon atoms, alkenyl having 3 to 8 carbon atoms, cycloalkyi having
5 to 10 carbon atoms, phenyl, phenyl which is substituted by alkyl having 1 to 4 carbon
atoms, or phenylalkyi having 1 to 4 carbon atoms in the alkyl moiety,
Tg is alkylene having 2 to 8 carbon atoms, alkenylene having 4 to 8 carbon atoms, alkynylene
having 4 carbon atoms, cyclohexylene, alkylene which has 2 to 8 carbon atoms and is
interrupted once or several times by -0-, or a radical of the formula -
CH2CH(OH)CH20TiiOCH2CH(OH)CH2- or -CH2-C(CH20H)2-CH2-,
T10 is alkylene which has 2 to 20 carbon atoms and can be interrupted once or several times
by -0-, or cyclohexylene,
Til is alkylene having 2 to 8 carbon atoms, alkylene which has 2 to 18 carbon atoms and is
interrupted once or several times by -0-, 1,3-cyclohexylene, 1,4-cyclohexylene, 1,3-
phenylene or 1,4-phenylene, or
T10 and Te, together with the two nitrogen atoms, are a piperazine ring;
in the compounds of formula (lie)
R'2 is Ci-Ci2alkyl and k is a number from 1 to 4;
in the compounds of the formula (III)
u is 1 or 2 and r is an integer from 1 to 3, the substituents

Yi independently of one another are hydrogen, hydroxyl, phenyl or halogen, halogenomethyl, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 18 carbon atoms, alkoxy having 1 to 18 carbon atoms which is substituted by a group -C00(Ci-Ci8alkyl); if u is 1,
Y2 is alkyl having 1 to 18 carbon atoms, phenyl which is unsubstituted or substituted by hydroxyl, halogen, alkyl or alkoxy having 1 to 18 carbon atoms;
alkyl which has 1 to 12 carbon atoms and is substituted by -COOH, -COOYs, -CONH2, -CONHY9, -CONY9Y10. -NH2, -NHYg, -NY9Y10, -NHCOY11, -CN and/or-OCOY11; alkyl which has 4 to 20 carbon atoms, is interrupted by one or more oxygen atoms and is unsubstituted or substituted by hydroxyl or alkoxy having 1 to 12 carbon atoms, alkenyl having 3 to 6 carbon atoms, glycidyl, cyclohexyl which is unsubstituted or substituted by hydroxyl, alkyl having 1 to 4 carbon atoms and/or -OCOYn, phenylalkyi which has 1 to 5 carbon atoms in the alkyl moiety and is unsubstituted or substituted by hydroxyl, chlorine and/or methyl, -COY12 or -SO2Y13, or, if u is 2,
Y2 is alkylene having 2 to 16 carbon atoms, alkenylene having 4 to 12 carbon atoms, xylylene, alkylene which has 3 to 20 carbon atoms, is interrupted by one or more -O- atoms and/or is substituted by hydroxyl, -CH2CH(OH)CH2-0-Yi5-OCH2CH(OH)CH2, -CO-Y16-CO-, -CO-NH-Y17-NH-CO- or -(CH2),n-C02-Yi8-OCO-(CH2)m. in which m is 1, 2 or 3,
Ys is alkyl having 1 to 18 carbon atoms, alkenyl having 3 to 18 carbon atoms, alkyl which has 3 to 20 carbon atoms, is interrupted by one or more oxygen or sulfur atoms or -NTe- and/or is substituted by hydroxyl, alkyl which has 1 to 4 carbon atoms and is substituted by -P(0)(OYi4)2, -NY9Y10 or -OCOY11 and/or hydroxyl, alkenyl having 3 to 18 carbon atoms, glycidyl, or phenylalkyi having 1 to 5 carbon atoms in the alkyl moiety, Y9 and Y10 independently of one another are alkyl having 1 to 12 carbon atoms, alkoxyalkyl having 3 to 12 carbon atoms, dialkylaminoalkyi having 4 to 16 carbon atoms or cyclohexyl having 5 to 12 carbon atoms, or Yg and Y10 together are alkylene, oxaalkylene or azaalkylene having in each case 3 to 9 carbon atoms, I Y11 is alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 18 carbon atoms or phenyl, Y12 is alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 18 carbon atoms, phenyl, alkoxy having 1 to 12 carbon atoms, phenoxy, alkylamino having 1 to 12 carbon atoms or phenylamino, Yi3 is alkyl having 1 to 18 carbon atoms, phenyl or alkylphenyl having 1 to 8 carbon atoms in

the alkyl radical,
Yi4 is all Yi5 is alkylene having 2 to 10 carbon atoms, phenylene or a group -phenylene-M-phenylene-
in which M is -0-, -S-, -SO2-, -CH2- or -C(CH3)2-,
Y16 is alkylene, oxaalkylene or thiaalkylene having in each case 2 to 10 carbon atoms,
phenylene or alkenylene having 2 to 6 carbon atoms,
Yi7 is alkylene having 2 to 10 carbon atoms, phenylene or alkylphenylene having 1 to 11
carbon atoms in the alkyl moiety, and
Y18 is alkylene having 2 to 10 carbon atoms or alkylene which has 4 to 20 carbon atoms and
is interrupted once or several times by oxygen;
in the compounds of the formula (IV) x is an integer from 1 to 3 and the substituents L
independently of one another are hydrogen, alkyl, alkoxy or alkylthio having in each case 1 to
22 carbon atoms, phenoxy or phenylthio.
5. A composition according to claim 1 wherein the UV-absorber of the class of hydroxyphenyl triazines is of formula (IV)

in which n is 1 or 2;
R^, R'^, R^ and R'^, independently of one another, are H, OH, C^-C^^^'M: C^-Cgalkenyl; C^-
C^ga'koxy; Cg-C^galkenoxy; halogen; trifluoromethyl; C^-C^^phenylalkyl; phenyl; phenyl which
is substituted by C^-C^galkyl, C^-C^galkoxy or halogen; phenoxy; or phenoxy which is
substituted by C^-C^galkyl, C^-C^galkoxy or halogen;
Rg and R^, independently of one another, are H, C^-C^j^lkyl; OR'^; Cg-Cgalkenyl; C^-

C18galkenoxy; halogen; trifluoromethyl; C^-C^^phenylalkyl; phenyl; phenyl which is substituted
by C1-C18galkyl, C1-C18galkoxy or halogen; phenoxy; or phenoxy which is substituted by C^-
C18galkyl, C1-C18galkoxy or halogen;
R6 is hydrogen, C1-C18alkyl, C2-C12cydoalkyl or C^-C^gPhenylalkyl;
R7, in the case where n = 1, and R7, independently of one another, are hydrogen or C -
C18galkyt; or are C^-C12aallkyl which is substituted by OH, C^-C^galkoxy, allyloxy, halogen, -
COOH, -COORg, -CONH^, -CONHRg, -CON(Rg)(R,^), -NH^, -NHRg, -N(Rg)(R^p), -NHCOR^^, -
CN, -OCOR^^, phenoxy and/or phenoxy which is substituted by C^-C^galkyl, C^-C^galkoxy or
halogen; or R^ is Cg-Cg^alkyl which is interrupted by -O- and may be substituted by OH; or R^
is Cg-Cgalkenyl; glycidyl; Cg-C^2 or -OCOR^^; C^-C^^phenylalkyl which is unsubstituted or substituted by OH, CI or CHg; -CO-
R^^or-SO^-R^g;
R^, in the case where n = 2, is C^-C^galkylene, C^-C^2^"^®"y'®"®' xylylene, Cg-C^Qalkylene
which is interrupted by O and/or substituted by OH, or is a group of the formula -
CH2CH(OH)CH20-R2o-OCH2CH(OH)CH2-, -CO-R^^-CO-, -CO-NH-R^^-NH-CO- or -(CH^)^-
COO-R -OOC-(CH,) -, in which m is a number in the range from 1 to 3, or is
23 ^ 2'm

Rg is C^-C^galkyl; C2-C^galkenyl; hydroxyethyl; Cg-CgQalkyI which is interrupted by O, NH, NRg or S and/or is substituted by OH; C^-C^alkyl which is substituted by -P(0)(OR^ J^- -^(^9X^10) or -OCOR^^ and/or OH; glycidyl; C5-C^2^y^'°^"^y' Phenyl; C^-C^^alkylphenyl or C^-C^^phenylalkyl;
Rg and R^^, independently of one another, are C^-C^g^lkyl; Cg-C^^^lkoxyalkyl; C^-C^gdialkylaminoalkyl or Cg-C^j^ycloalkyl, or Rg and R^^ together are Cg-Cgalkylene or -oxaalkylene or -azaalkylene;
R^^ is C^-C,galkyl; C^-C^galkenyl or phenyl; C^-C^g'^ydroxyalkyl; cyclohexyl; or is Cg-Cggalkyl which is interrupted by -O- and may be substituted by OH;
R^2 is C^-C^galkyl; C^-C^galkenyl; phenyl; C^-C^galkoxy; Cg-C^galkenyloxy; Cg-CgQalkoxy which is interrupted by O, NH, NRg or S and/or substituted by OH; cyclohexyloxy; C^-C^^alkylphenoxy; C^-C^^phenylalkoxy; phenoxy; C^-C^^^lkylamino; phenylamino; tolylamino or naphthylamino; R^3 is C^-C^g^lkyl; phenyl; naphthyl or C^-C^^alkylphenyl;










7. A composition according to claim 1 wherein the sterically hindered amine is selected from
the group consisting of 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-
piperidyI)-1,2,3,4-butanetetracarboxylate, 1,1'-(1.2-ethanediyl)-bis(3,3,5,5-tetrame-
thylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethyl-piperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)-malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, bis(1-octyl-oxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succi-nate, 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-triazine 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-triazine and 1,2-bis(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetrame-thyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 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'-bls(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-tri-chloro-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-dibutyiamine and 4-butylamino-2,2,6,6-tetramethylpiperidlne (CAS Reg. No.

[192268-64-7]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-clodecylsuccinimide, N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-di-aza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro-[4,5]decane and epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ethene, N,N'-bis-formyl-N,N'-bis(2,2,6,6-tetrame-thyl-4-piperidyl)hexamethylenediamine, 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 and the compound of example 2 of US-6117995 .


wherein R301, R302 and R303 are independently C10-C36alkyl;
R304, R305 and R306 are independently Cg-CsealkyI;
R310 and R311 are independently hydrogen or Ci-Cisaikyi;
R307 and R308 are independently Ci-Caalkylene;
k is a number from
n is a number from 2 to 20;
m is a number from 4 to 20; and
X, y independently are numbers from 3 to 20.
9. A composition according to claim 8 wherein the tertiary amine is a compound of formula
(a).
10. A composition according to claim 1 wherein the tertiary amine is present in an amount of 0.1-2% by weight, based on the weight of the thermoplastic polymer.
11. A composition according to claim 1 wherein the UV-absorber is present in an amount of 0.01-2% by weight, based on the weight of the thermoplastic polymer.
12. A composition according to claim 1 wherein the sterically hindered amine is present in an amount of 0.01-2% by weight, based on the weight of the thermoplastic polymer.
13. A composition according to claim 1 wherein the total amount of tertiary amine, UV-absorber and/or sterically hindered amine is from 0.2 to 4% by weight based on the weight of the thermoplastic polymer.
14. A composition according to claim 1, which contains additionally a further stabilizer selected from the group consisting of a phenolic antioxidant, a phosphite or phosphonite and benzofuranone or indolinone.
15. A method for the stabilization of a non halogen containing thermoplastic polymer
comprising incorporating into the non halogen containing thermoplastic polymer
an aliphatic tertiary amine with a molecular weight greater than 400 g/mol, which is not a 2,2,6,6 tetramethylpiperidine derivative:

a UV-absorber selected from the group consisting of the hydroxyphenyl benzotriazoles, hydroxyphenyl triazines, hydroxy benzophenones and oxalic anilides; or a light stabilizer from the class of sterically hindered amines; or a a mixture of the UV-absorber and the sterically hindered amine.
16. Use of an aliphatic tertiary amine with a molecular weight greater than 400 g/mol, which
is not a 2,2,6,6 tetramethylpiperidine derivative; and
a UV-absorber selected from the group consisting of the hydroxyphenyl benzotriazoles,
hydroxyphenyl triazines, hydroxy benzophenones and oxalic anilides; or
a light stabilizer from the class of sterically hindered amines; or a
a mixture of the UV-absorberand the sterically hindered amine
for the stabilization of non halogen containing thermoplastic polymers.









Documents:

http://ipindiaonline.gov.in/patentsearch/GrantedSearch/viewdoc.aspx?id=6SnwK0GTpi+wSjak5+SQOA==&loc=egcICQiyoj82NGgGrC5ChA==


Patent Number 277204
Indian Patent Application Number 4026/CHENP/2008
PG Journal Number 48/2016
Publication Date 18-Nov-2016
Grant Date 15-Nov-2016
Date of Filing 31-Jul-2008
Name of Patentee BASF SE
Applicant Address 67056, LUDWIGSHAFEN, GERMANY
Inventors:
# Inventor's Name Inventor's Address
1 LORENZETTI, CESARE, VIA GUGLIELMO MARCONI, 126, I-63013 GROTTAMMARE (AP),
2 BONORA, MICHELA, VIA VOLONTARI DELLA LIBERTA 9, I-40135 BOLOGNA,
3 BASSI, ANNA, VIA VOLTERRA, 6, I-40135 BOLOGNA,
4 ROSSI, MIRKO, VIA GRAMSCI, 4, I-40068 SAN LAZZARO DI SAVENA (BO),
PCT International Classification Number C08K5/00
PCT International Application Number PCT/EP07/50579
PCT International Filing date 2007-01-22
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 6101123.5 2006-02-01 EUROPEAN UNION