Synergistic combinations of nano-scaled fillers and hindered amine light stabilizers Number:7,084,197 from the United States Patent and Trademark Office (PTO) owispatent Polymer compositions comprising a polymeric substrate and an effective stabilizing amount of a synergistic mixture of a nano-scaled filler and at least one additive selected from the group consisting of the hindered amine light stabilizers are effectively stabilized against the deleterious effects of oxidative, thermal or light-induced degradation.<H combinations, stabilizers, Synergistic, com, 7084197.html, Patent, pto, 7084197

Title: Synergistic combinations of nano-scaled fillers and hindered amine light stabilizers

Abstract: Polymer compositions comprising a polymeric substrate and an effective stabilizing amount of a synergistic mixture of a nano-scaled filler and at least one additive selected from the group consisting of the hindered amine light stabilizers are effectively stabilized against the deleterious effects of oxidative, thermal or light-induced degradation.

Patent Number: 7,084,197 Issued on 08/01/2006 to Chin, et al.

Inventors: Chin; Hui (Katonah, NY); Solera; Peter Shelsey (Suffern, NY); Horsey; Douglas Wayne (Briarcliff Manor, NY); Kaprinidis; Nikolas (New York City, NY)
Assignee: Ciba Specialty Chemicals Corporation (Tarrytown, NY)

Appl. No.: 10/480,870

Filed: June 20, 2002

PCT Filed: June 20, 2002

PCT No.: PCT/EP02/06847

371(c)(1),(2),(4) Date: August 13, 2004

PCT Pub. No.: WO03/002651

PCT Pub. Date: January 09, 2003

Current U.S. Class: 524/99 ; 524/100; 524/102; 524/103; 524/445; 524/447

Current International Class: C08K 5/3412 (20060101); C08K 3/34 (20060101)

Field of Search: 524/99-100,102-103,445-447 522/75-79

References Cited [Referenced By]

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4467061	August 1984	Yamamoto et al.
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6087433	July 2000	Hanada et al.
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6146557	November 2000	Inata et al.
6156838	December 2000	Yoshikawa et al.
6344506	February 2002	Vasseur
6353037	March 2002	Thunhorst et al.
6387981	May 2002	Zhang et al.
6423768	July 2002	Khouri
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6579926	June 2003	Patel
6593392	July 2003	Wang
6605655	August 2003	Kato et al.
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6833392	December 2004	Acquarulo et al.
6849680	February 2005	Knudson et al.
6861481	March 2005	Ding et al.

Foreign Patent Documents


2247681	Mar., 1992	GB
99/02590	Jan., 1999	WO
99/41299	Aug., 1999	WO

Other References

Derwent Abstract 1990-181491 [25] for JP 02117934 (1990). cited by other .
Patent Abstracts of Japan Publication No. 09078025 (1997). cited by other .
R. Gachter et al., Plastics Additives Handbook, 4.sup.th Ed., pp. 525-591, (1990). cited by other.

Primary Examiner: Szekely; Peter
Attorney, Agent or Firm: Stevenson; Tyler A.

Parent Case Text

This is a 371 of PCT/EP02/06847, filed Jun. 20, 2002, which claims benefit of U.S. provisional application No. 60/302,125, filed Jun. 29, 2001.

Claims

What is claimed is:

1. A polyamide composition, stabilized against the deleterious effects of oxidative, thermal or light-induced degradation, which composition comprises (a) a polyamide substrate, (b) at least one nano-scaled filler with a platelet structure where the platelets have a thickness below 2 nm, and (c) a 1:1 mixture of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate and the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine).

2. A composition according to claim 1, wherein the filler is an organophilic phyllosilicate, a naturally occuring phyllosilicate, a synthetic phyllosilicate or a mixture of such phyllosilicates.

3. A composition according to claim 1, in which component (b) is present in an amount of 0.5 to 10% by weight, based on the weight of component (a).

4. A composition according to claim 1, in which component (c) is present in an amount of 0.01 to 10% by weight, based on the weight of component (a).

5. A composition according to claim 1, further comprising (d) at least one additive selected from the group consisting of additional hindered amine light stabilizers, ultraviolet light absorbers, phenolic antioxidants, organic phosphorus stabilizers, aminic antioxidants, hydroxylamine stabilizers, nitrone stabilizers, benzofuranone stabilizers and amine oxide stabilizers.

6. A process for effectively stabilizing a polyamide substrate subject to the deleterious effects of oxidative, thermal or light-induced degradation, which process comprises incorporating into a polyamide substrate an effective stabilizing amount of (b) at least one nano-scaled filler with a platelet structure where the platelets have a thickness below 2 nm and (c) a 1:1 mixture of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate and the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine).

7. A flame retardant polyamide composition which comprises (a) a polyamide substrate, (b) at least one nano-scaled filler with a platelet structure where the platelets have a thickness below 2 nm, (c) a 1:1 mixture of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate and the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and (d) at least one compound selected from the group consisting of brominated flame retardants, phosphorus containing flame retardants and inorganic flame retardants.

8. A polyamide composition according to claim 1 in which the polyamide is polyamide 6,6.

Description

The present invention relates to novel polymer compositions comprising a polymeric substrate, stabilized against the deleterious effects of oxidative, thermal or light-induced degradation, and an effective stabilizing amount of a synergistic mixture of a nano-scaled filler and at least one additive selected from the group consisting of the hindered amine light stabilizers.

The addition of fillers to organic materials, especially polymers, is known and is described for example in R. Gachter, H. Muller (Eds.), Plastics Additives Handbook, 3rd ed., pages 525 591, Hanser Publishers, Munich 1990. The use of fillers in polymers has the advantage that it is possible to bring about improvement in, for example, the mechanical properties, especially the density, hardness, rigidity or impact strength of the polymer. Since the fillers are often less expensive than the pure polymers, the replacement of part of the expensive pure polymers by fillers also leads to a reduction in the cost of the polymer.

With incorporation of nano-scaled fillers, the mechanical properties of polymers can be improved at a much lower concentration of 5 to 10% by weight compared to 20 to 50% by weight with the micro-scaled normal filler particles. Polymers containing nano-scaled fillers show improved surface qualities like gloss, lower tool wear at processing and better conditions for recycling.

Polymer compositions comprising nano-scaled fillers, or nanocomposites, exhibit properties such as good surface appearance, toughness, ductility and tensile strength. However, such polymer compositions do not have long-term stability equal to compositions that comprise traditional micro-scaled fillers. Long-term stability is for example measured by color change or gloss change on long-term aging under exposure to heat, oxygen and light.

WO-A-99/41299 is aimed at a polymer nanocomposite composition of a polyamide and a treated silicate.

WO-A-01/04197 discloses a polyamide composition comprising one or more polyamide polymers or copolymers, one or more layered clay materials, and one or more alkoxylated ammonium cations.

It has now been found that polymeric substrates are stabilized against the deleterious effects of oxidative, thermal or light-induced degradation by incorporation therein of an effective stabilizing amount of a synergistic mixture of a nano-scaled filler and at least one additive selected from the group consisting of the hindered amine light stabilizers. Surprisingly, polymer compositions comprising normal use levels of nano-scaled fillers and at least one additive selected from the group consisting of the hindered amine light stabilizers, upon long-term aging under exposure to heat and light, perform about as well as polymer compositions that comprise normal use levels of traditional micro-scaled fillers and at least one additive selected from the group consisting of the hindered amine light stabilizers.

The instant invention pertains to a polymer composition, stabilized against the deleterious effects of oxidative, thermal or light-induced degradation, which composition comprises (a) a polymer substrate, (b) at least one nano-scaled filler and (c) at least one additive selected from the group consisting of the hindered amine light stabilizers.

The polymer substrates of component (a) are natural or synthetic polymers or copolymers. The substrates of component (a) are for example synthetic polymers, in particular thermoplastic polymers such as polyamides and polyolefins. Polyolefins are for instance polypropylene or polyethylene.

Suitable polymer substrates of component (a) are for example:

1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, poly-but-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods: a) radical polymerization (normally under high pressure and at elevated temperature). b) catalytic polymerization using a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either .pi.- or .sigma.-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium (III) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalysts can be used by themselves in the polymerization or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, IIa and/or IIIa of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

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 copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, ethylene/vinylcyclohexane copolymers, ethylene/cycloolefin copolymers (e.g. ethylene/norbornene like COC), ethylene/1-olefins copolymers, where the 1-olefin is generated in-situ; propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/vinylcyclohexene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EM), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.

4. Hydrocarbon resins (for example C.sub.5 C.sub.9) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.

Homopolymers and copolymers from 1.) 4.) may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.

5. Polystyrene, poly(p-methylstyrene), poly(.alpha.-methylstyrene).

6. Aromatic homopolymers and copolymers derived from vinyl aromatic monomers including styrene, .alpha.-methylstyrene, all isomers of vinyl toluene, especially p-vinyltoluene, all isomers of ethyl styrene, propyl styrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene, and mixtures thereof. Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.

6a. Copolymers including aforementioned vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene/butadiene, styrene/acrylonitrile, styrene/ethylene (interpolymers), styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/styrene.

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, isotactic, 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 .alpha.-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, SAN, MBS, ASA or AES polymers.

8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfo-chlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.

9. Polymers derived from .alpha.,.beta.-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.

10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrile/butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/alkyl methacrylate/butadiene terpolymers.

11. Polymers derived from unsaturated alcohols and amines or the acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.

12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.

15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.

16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).

17. Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.

18. Polyesters derived from dicarboxylic acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS. Polyesters and polyester copolymers as defined in U.S. Pat. No. 5,807,932 (column 2, line 53), incorporated herein by reference.

19. Polycarbonates and polyester carbonates.

20. Polyketones.

21. Polysulfones, polyether sulfones and polyether ketones.

22. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melamines on the other hand, such as phenol/formaldehyde resins, urea/formaldehyde resins and melamine/formaldehyde resins.

23. Drying and non-drying alkyd resins.

24. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.

25. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates.

26. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.

27. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.

28. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.

29. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC/ASA, PC/PBT, PVC/CPE, PVC/acrylates, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.

30. Naturally occurring and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, typically those used as spinning compositions, as well as aqueous emulsions of such materials.

31. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or latices of carboxylated styrene/butadiene copolymers.

32. Polysiloxanes such as the soft, hydrophilic polysiloxanes described, for example, in U.S. Pat. No. 4,259,467; and the hard polyorganosiloxanes described, for example, in U.S. Pat. No. 4,355,147.

33. Polyketimines in combination with unsaturated acrylic polyacetoacetate resins or with unsaturated acrylic resins. The unsaturated acrylic resins include the urethane acrylates, polyether acrylates, vinyl or acryl copolymers with pendant unsaturated groups and the acrylated melamines. The polyketimines are prepared from polyamines and ketones in the presence of an acid catalyst.

34. Radiation curable compositions containing ethylenically unsaturated monomers or oligomers and a polyunsaturated aliphatic oligomer.

35. Epoxymelamine resins such as light-stable epoxy resins crosslinked by an epoxy functional coetherified high solids melamine resin such as LSE-4103 (Monsanto).

The polymer substrates of component (a) are in particular selected from the group consisting of thermoplastic polymers, for example polyamides or polyolefins. Polyolefins are for instance polyethyelene and polypropylene.

A component (a) of special interest is a polyamide a thermoplastic polyolefin like for example polypropylene or polyethylene; ABS or high impact polystyrene (HIPS).

Nano-scaled fillers are also referred to as "nanoclays" are disclosed for example in U.S. Pat. Nos. 5,853,886 and 6,020,419, the relevant disclosures of which are hereby incorporated by reference.

Nano-scaled fillers of the present invention are for example phyllosilicates or smectite clays, for example organophilic phyllosilicates, naturally occuring phyllosilicates, synthetic phyllosilicates or a mixture of such phyllosilicates. The present nano-scaled fillers are for example montmorillonites, bentonites, beidellites, hectorites, saponites or stevensites.

For example, nano-scaled montmorillonites have a "platey" or platelet structure. The platelets generally have a thickness below about 2 nm. The platelets or particles generally have an average diameter between 20 and 30,000 nm, and a ratio of length to width of between 30,000:1 and 20:1. Commercially available nano-scaled montmorillonites of such structure are Nanomer.RTM. I.42E, available from Nanocor, and Cloisite.RTM. 30B, available from Southern Clay.

Nano-scaled fillers possess an extremely large surface with high surface energy. The deactivation of the surface energy and the compatibilization of the nano-scaled fillers with a polymer is therefore even more important than with a common micro-scaled filler in order to avoid coagulation and reach an excellent dispersion of the nano-scaled filled in the polymer. The nano-scaled fillers like the phyllosilicates are made organophilic by ion exchange, for example with alkylammonium salts. Such nano-scaled organophilic phyllosilicates are better swellable and easier to disperse in a polymer matrix.

Treated nano-scaled fillers are also referred to as "treated layered clay material" or "organoclay".

The nano-scaled filler of component (b) is present in the compositions of the present invention at a concentration of 0.5 to 10% by weight, based on the weight of component (a), for example, 1 to 9% by weight, for instance 3 to 7% by weight, for example 5% by weight, based on the weight of component (a).

The hindered amine light stabilizers (HALS) of component (c) are selected from the group consisting of hindered amines substituted on the N-atom by an alkoxy or cycloalkoxy moiety, hindered amines substituted on the N-atom by an alkoxy which is further substituted with an hydroxy group, and conventional hindered amines where the N-atom is substituted by hydrogen, alkyl, acyl and the like.

Alkoxy is a branched or straight chain radical having up to 25 carbon atoms, for example methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, decyloxy, tetradecyloxy, hexadecyloxy or octadecyloxy. Present alkoxy may have from 1 to 12, for instance from 1 to 8, e.g. from 1 to 6, carbon atoms.

Cycloalkoxy is for example C.sub.5 C.sub.12cycloalkoxy, for example cyclopentyloxy or cyclohexyloxy.

Alkyl is a branched or straight chain radical having up to 25 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, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n-octyl, 2-ethylhexyl, 1,1,3-tri-methylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, icosyl or docosyl.

The hindered amines substituted on the N-atom by an alkoxy or a cycloalkoxy moiety are well known in the art. These are described in detail in U.S. Pat. No. 5,204,473, the relevant parts of which are incorporated herein by reference.

The hindered amines substituted on the N-atom by an alkoxy, cycloalkoxy or benzyloxy moiety which are useful in the instant invention include the following: bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine; 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-6-- (2-hydroxyethyl-amino-s-triazine; bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate; the oligomeric compound which is the condensation product of 4,4'-hexamethylenebis(amino-(1-octyloxy-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butylam- ino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine; the oligomeric compound which is the condensation product of 4,4'-hexamethylenebis(amino-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin- e)) and 2,4-dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl- )butylamino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine; the oligomeric compound which is the condensation product of 4,4'-hexamethylenebis(amino-(1-propyloxy-2,2,6,6-tetramethylpiperidine)) and 2,4-dichloro-6-[(1-propyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butyla- mino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine (the n-propoxy derivative of the corresponding N--H hindered amine below); the oligomeric compound which is the condensation product of 4,4'-hexamethylenebis(amino-(1-acetoyloxy-2,2,6,6-tetramethylpiperidine)) and 2,4-dichloro-6-[(1-acetoyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butyl- amino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine; 1-methoxy-4-hydroxy-2,2,6,6-tetramethylpiperidine; 1-octyloxy-4-hydroxy-2,2,6,6-tetramethylpiperidine; 1-cyclohexyloxy-4-hydroxy-2,2,6,6-tetramethylpiperidine; 1-methoxy-4-oxo-2,2,6,6-tetramethylpiperidine; 1-octyloxy-4-oxo-2,2,6,6-tetramethylpiperidine; 1-cyclohexyloxy-4-oxo-2,2,6,6-tetramethylpiperidine; bis(1-heptyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(1-nonyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(1-dodecyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; N,N',N'',N'''-tetrakis[(4,6-bis(butyl-1-octyloxy-2,2,6,6-pentamethylpiper- idin-4-yl)-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane; and

##STR00001##

This specific hydrocarbyloxy hindered amine stabilizer, CAS # 191680-81-6, is described in U.S. Pat. No. 5,844,026.

The hindered amines substituted on the N-atom by a hydroxy-substituted alkoxy moiety which are useful in the instant invention include the following: 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperi- dine; 1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidin- e; 1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethylpiperidine; bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-- 4-yl) adipate; bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl) succinate; bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)gluta- rate; and 2,4-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpipe- ridin-4-yl]-N-butylamino}-6-(2-hydroxyethylamino)-s-triazine.

Conventional hindered amines useful in the present invention include the following: the oligomeric compound which is the condensation product of 4,4'-hexamethylenebis-(amino-(2,2,6,6-tetramethylpiperidine)) and 2,4-dichloro-6-[(2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine; bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate; polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine); polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid; polycondensation product of 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and 1,2-dibromoethane; mixture of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate and the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine); mixture of the polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid with the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine); bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate; di(1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate; 4-benzoyl-2,2,6,6-tetramethylpiperidine; 4-stearyloxy-2,2,6,6-tetramethylpiperidine; tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate; tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) 1,2,3,4-butanetetracarboxylate; tetrakis(1,2,2,6,6-pentamethylpiperidin-4-yl) 1,2,3,4-butanetetracarboxylate; polycondensation product of 2,4-dichloro-6-morpholino-s-triazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine); polycondensation product of 2,4-dichloro-6-morpholino-s-triazine and 4,4'-hexamethylenebis(amino-(1-methyl-2,2,6,6-tetramethylpiperidine)); N,N',N'',N'''-tetrakis[(4,6-bis(butyl-1,2,2,6,6-pentamethylpiperidin-4-yl- )-amino-s-triazin-2-yl]-1,10-diamino-4,7-diazadecane; octamethylene bis(2,2,6,6-tetramethylpiperidin-4-carboxylate); N-2,2,6,6-tetramethylpiperidin-4-yl-n-dodecylsuccinimide; N-1,2,2,6,6-pentamethylpiperidin-4-yl-n-dodecylsuccinimide; N-1-acetyl-2,2,6,6-tetramethylpiperidin-4-yln-dodecylsuccinimide; 4-C.sub.15 C.sub.17alkanoyloxy-2,2,6,6-tetramethylpiperidine; polycondensation product of 2,4-dichloro-6-cyclohexylamino-s-triazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine); 1,5-bis(2,2,6,6-tetramethylpiperidin-4-yl)-1,5-diaza-4-oxopropane; copolymer of methyl methracrylate, ethyl acrylate and 2,2,6,6-tetramethylpiperidin-4-yl acrylate; copolymer of N-octadecylmaleimide, styrene and N-(2,2,6,6-tetramethylpiperidin-4yl)maleimide; 1,3,5-tris[3-(2,2,6,6-piperidin-4-ylamino)-2-hydroxy-propyl)isocyanurate; olefin copolymer containing units derived from N-[2-(2,2,6,6-tetramethylpiperidin-4-yl)oxalamid-1-yl]maleimide; 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5,1,11,2]heneicosane; C.sub.12 C.sub.14alkyl 3-(2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5,1,11,2]heneicosa- ne-20-yl)propionate; reaction product of epichlorohydrin and 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5,1,11,2]heneicosane; 1,3-di(2,2,6,6-tetramethylpiperidin-4-yl) 2,4-ditridecyl butanetetracarboxylate; 1,3-di(1,2,2,6,6-pentamethylpiperidin-4-yl) 2,4-ditridecyl butanetetracarboxylate; polycondensation product of 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]-undecane- , tetramethyl 1,2,3,4-butanetetra-carboxylate and 2,2,6,6-tetramethyl-4-hydroxypiperidine; polycondensation product of 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4,8,10-tetraoxaspiro[5.5]-undecane- , tetramethyl 1,2,3,4-butanetetra-carboxylate and 1,2,2,6,6-pentamethyl-4-hydroxypiperidine; 1,4-bis(2,2,6,6-tetramethylpiperidin-4-yl)-2,2-dimethyl-1,4-diaza-4-oxopr- opane; reaction product of 4-amino-2,2,6,6-tetramethylpiperidine and tetramethylolacetylenediurea; 1,6-hexamethylenebis[N-formyl-N-(2,2,6,6-tetramethylpipeidin-4-yl)amine]; copolymer of N-(2,2,6,6-tetramethylpiperdin-4-yl)maleimide and a C.sub.20 C.sub.24-alpha-olefin; poly[3-(2,2,6,6-tetramethylpiperidin-4-yloxy)propyl-methyl-siloxane]; polycondensation product of 2,4-dichloro-6-[N-butyl-N-(2,2,6,6-tetramethylpiperidin-4-yl)amino]-s-tri- azine and 1,10-diamino-4,7-diazadecane; dodecyl 3-(2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5,1,11,2]heneicosa- ne-20-yl)propionate;

##STR00002## n is a number from the range from 2 to 200; and

##STR00003##

For instance, the hindered amines useful in the present invention include: the oligomeric compound which is the condensation product of 4,4'-hexamethylenebis(amino-(1-propyloxy-2,2,6,6-tetramethylpiperidine)) and 2,4-dichloro-6-[(1-propyloxy-2,2,6,6-tetramethylpiperidin-4-yl)butyla- mino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine (the n-propoxy derivative of the corresponding N--H hindered amine below);

##STR00004## the oligomeric compound which is the condensation product of 4,4'-hexamethylenebis(amino-(2,2,6,6-tetramethylpiperidine)) and 2,4-dichloro-6-[(2,2,6,6-tetramethylpiperidin-4-yl)butylamino]-s-triazine end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine; bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate; polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine); polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid; mixture of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate and the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine); mixture of the polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid with the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine); bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate; di(1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate; polycondensation product of 2,4-dichloro-6-morpholino-s-triazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine); polycondensation product of 2,4-dichloro-6-morpholino-s-triazine and 4,4'-hexamethylenebis(amino-(1-methyl-2,2,6,6-tetramethylpiperidine)); N,N',N'',N'''-tetrakis[(4,6-bis(butyl-1,2,2,6,6-pentamethylpiperidin-4-yl- )-amino-s-triazin-2-yl]1,10-diamino-4,7-diazadecane;

##STR00005## n is a number from the range from 2 to 200; and

##STR00006##

Preferably, component (c) is a 1:1 mixture of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate and the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine).

It is contemplated that mixtures of the N-alkoxy or cyclohexyloxy substituted hindered amines; mixtures of the N-hydroxy-alkoxy substituted hindered amines; and mixtures of these two types of hindered amines can be used in the instant invention. Indeed, mixtures of these types of hindered amines along with conventional hindered amines where the N-atom is substituted by hydrogen, alkyl, acyl and the like are also contemplated as being useful in this invention.

Additionally, the stabilized composition may also include at least one stabilizer selected from the group consisting of additional hindered amine light stabilizers, ultraviolet light absorbers, phenolic antioxidants, organic phosphorus stabilizers, aminic antioxidants, hydroxylamine stabilizers, nitrone stabilizers, benzofuranone stabilizers and amine oxide stabilizers.

Accordingly, the instant invention also pertains to a polymer composition, stabilized against the deleterious effects of oxidative, thermal or light-induced degradation, which composition comprises (a) a polymer substrate, (b) at least one nano-scaled filler, (c) at least one additive selected from the group consisting of the hindered amine light stabilizers, and (d) at least one additive selected from the group consisting of additional hindered amine light stabilizers, ultraviolet light absorbers, phenolic antioxidants, organic phosphorus stabilizers, aminic antioxidants, hydroxylamine stabilizers, nitrone stabilizers, benzofuranone stabilizers and amine oxide stabilizers.

The ultraviolet light absorbers (UVA's or UV absorbers), of component (d) are for example selected from the group consisting of benzotriazole, benzophenone, .alpha.-cyanoacrylate, oxanilide, s-triazine, cinnamate, malonate, benzoate, salicylate and benzoxazin-4-one ultraviolet light absorbers.

The UV absorbers of component (d) are for example selected from the group consisting of benzotriazole, benzophenone and s-triazine ultraviolet light absorbers.

The UV absorbers are well known in the field of stabilization of substrates from degradation caused by exposure to actinic radiation. Examples of UV absorbers which may be used in the present invention include the following: a) 4-octyloxy-2-hydroxybenzophenone; b) 4-methoxy-2-hydroxybenzophenone; c) 2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole; d) 2-(2-hydroxy-5-tert-octylphenyl-2H-benzotriazole; e) 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole; f) octyl 3-(benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate; g) 2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole; h) 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole; i) 5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole; j) 5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole; k) 2-(2-hydroxy-3-sec-butyl-5-tert-butylphenyl)-2H-benzotriazole; l) 2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole; m) 2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole; n) 2-[2-hydroxy-3,5-di(.alpha.,.alpha.-dimethylbenzyl)phenyl]-2H-benzotriazo- le; o) 2-[2-hydroxy-3-(.alpha.,.alpha.-dimethylbenzyl)-5-tert-octylphenyl]- -2H-benzotriazole; p) 2-{(2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)- ethyl]phenyl}-2H-benzotriazole; q) 2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-benzot- riazole; r) 2-ethylhexyl p-methoxycinnamate; s) 4-methoxy-2,2'-dihydroxybenzophenone; t) 4,4'dimethoxy-2,2'-dihydroxybenzophenone; u) 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine; v) 2,4-diphenyl-6-(2-hydroxy-4-hexyloxyphenyl)-s-triazine; w) 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-tridecyloxy-2-hydroxypropox- y)phenyl]-s-triazine; and x) 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-tridecyloxy-2-hydroxypropox- y)-5-.alpha.-cumylphenyl]-s-triazine.

In another embodiment, the UV absorber is a) 4-octyloxy-2-hydroxybenzophenone; b) 4-methoxy-2-hydroxybenzophenone; d) 2-(2-hydroxy-5-tert-octylphenyl-2H-benzotriazole; o) 2-[2-hydroxy-3-(.alpha.,.alpha.-dimethylbenzyl)-5-tert-octylphenyl]-2H-be- nzotriazole; p) 2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)e- thyl]phenyl}-2H-benzotriazole; or q) 2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-benzot- riazole.

Hydroxylamine stabilizers are disclosed for example in U.S. Pat. Nos. 4,590,231; 4,612,393; 4,649,221; 4,668,721; 4,691,015; 4,696,964; 4,703,073; 4,720,517; 4,757,102; 4,782,105; 4,831,134; 4,876,300; 5,006,577; 5,019,285; 5,064,883; 5,185,448 and 5,235,056.

Nitrone stabilizers are described in U.S. Pat. No. 4,898,901.

A specific amine oxide is for example Genox.TM. EP, a di(C.sub.16 C.sub.18)alkyl methyl amine oxide, CAS# 204933-93-7.

For example U.S. Pat. Nos. 4,666,962; 4,666,963; 4,678,826; 4,753,972; 4,757,102; 4,760,179; 4,929,657; 5,057,563; 5,021,479; 5,045,583 and 5,185,448 disclose the use of various substituted hydroxylamine stabilizers towards the stabilization of organic materials.

For example U.S. Pat. Nos. 5,081,300; 5,162,408; 5,844,029; 5,880,191 and 5,922,794 disclose saturated hydrocarbon amine oxide stabilizers.

The benzofuranone stabilizers are those disclosed for example in U.S. Pat. Nos. 4,325,863; 4,338,244; 5,175,312; 5,216,052; 5,252,643; 5,369,159; 5,488,117; 5,356,966; 5,367,008; 5,428,162; 5,428,177; 5,614,572; 5,883,165 or 5,516,920, all incorporated herein by reference, or 3-(4-(2-acetoxyethoxy)phenyl)-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3-(4-(2-stearoyloxyethoxy)phenyl)benzofuran-2-one, 3,3'-bis(5,7-di-tert-butyl-3-(4-(2-hydroxyethoxy)phenyl)benzofuran-2-one)- , 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one, 3-(2,3-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one.

Examples of such antioxidants and hydroxylamines include the following: 4,4'-di-.alpha.-cumyl-diphenylamine (CAS # 10081-67-1) mono- and dialkylated tert-butyl/tert-octyl-diphenylamines (IRGANOX.RTM. L57), n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinammate), di-n-octadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, thiodiethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 3,6-dioxaoctamethylene bis(3-methyl-5-tert-butyl-4-hydroxyhydrocinnamate), 2,6-di-tert-butyl-p-cresol, 2,2'-ethylidene-bis(4,6-di-tert-butylphenol), 1,3,5-tris(2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) isocynurate, 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)ethyl]isocyanu- rate, 3,5-di-(3,5-di-tert-butyl-4-hydroxybenzyl)mesitol, hexamethylene bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), 1-(3,5-di-tert-butyl-4-hydroxyanilino)-3,5-di(octylthio)-s-triazine, N,N'-hexamethylene-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), calcium bis(ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate), ethylene bis[3,3-di(3-tert-butyl-4-hydroxyphenyl)butyrate], octyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate, bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazide, N,N'-bis[2-(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyloxy)-ethyl]oxamide, and N,N-dialkylhydroxylamine prepared from di(hydrogenated tallow)amine by direct oxidation.

For example, the phenolic antioxidant is neopentanetetrayl tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamate), n-octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 2,6-di-tert-butyl-p-cresol or 2,2'-ethylidene-bis(4,6-di-tert-butylphenol).

The effective amount of component (c), in combination with the optional stabilizers selected from additional hindered amine light stabilizers, ultraviolet light absorbers, phenolic antioxidants, organic phosphorus stabilizers, aminic antioxidants, hydroxylamine stabilizers, nitrone stabilizers, benzofuranone stabilizers and amine oxide stabilizers, in the present compositions is 0.01 to 10% by weight based on the weight of component (a); for example 0.1 to 2% by weight based on the polymer of component (a), for instance 0.1 to 1.0% by weight based on component (a).

Further in addition to component (b), the present stabilized compositions may comprise other traditional additives selected from, for example, other antioxidants, other UV absorbers, other hindered amines, other phosphites or phosphonites, benzofuran-2-ones, thiosynergists, polyamide stabilizers, metal stearates, nucleating agents, fillers, reinforcing agents, lubricants, emulsifiers, dyes, pigments, optical brighteners, flame retardants, antistatic agents, blowing agents and the like, such as the materials listed below, or mixtures thereof. These optional further additives are present from 0.01 to 10% by weight; preferably from 0.025 to 5% by weight, and most preferably from 0.1 to 3% by weight, based on the total weight of the composition.

These other traditional additives are selected from, for example:

1. Antioxidants

1.1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 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.

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.

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.

1.4. Tocopherols, for example .alpha.-tocopherol, .beta.-tocopherol, .gamma.-tocopherol, .delta.-tocopherol and mixtures thereof (Vitamin E).

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.

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-methyl-phenyl)-3-n-dodecylmercaptobutane- , ethylene glycol bis[3,3-bis(3-tert-butyl-4-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methyl-phenyl)dicyclopentadiene, bis[2-(3'tert-butyl-2-hydroxy-5-methylbenzyl)-6-tert-butyl-4-methylphenyl- ]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.

1.7. 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-butyl-benzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, 1,3,5-tri-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, di-(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 3,5-di-tert-butyl-4-hydroxybenzyl-mercapto-acetic acid isooctyl ester, bis-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol terephthalate, 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, 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid dioctadecyl ester and 3,5-di-tert-butyl-4-hydroxybenzyl-phosphoric acid monoethyl ester, calcium-salt.

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)malona- te, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hy- droxybenzyl)malonate.

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.

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-hydroxybenzyl)isocyanurate.

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.

1.12. Acylaminophenols, for example 4-hydroxy-lauric acid anilide, 4-hydroxy-stearic acid anilide, 2,4-bis-octylmercapto-6-(3,5-tert-butyl-4-hydroxyanilino)-s-triazine and octyl-N-(3,5-di-tert-butyl-4-hydroxyphenyl)-carbamate.

1.13. Esters of .beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

1.14. Esters of .beta.-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

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.

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.

1.17. Amides of .beta.-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid e.g. N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenedia- mide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediam- ide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxami- de (Naugard.RTM.XL-1 supplied by Uniroyal).

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-phenlenediamine, 4-(p-toluenesulfamoyl)diphenylamine, N,N'-dimethyl-N,N'-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyidiphenylamine, 4-isopropoxy-diphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p,p'-di-tert-octyldiphenylamine, 4-n-butyrylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphen