Light stabilizer mixture

Abstract

This invention relates to a stabilizer mixture comprising a sterically hindered amine light stabilizer, a triUV absorber, and a diphenyl ketone UV absorber.

Description

[Summary of the Invention]

[0001] This invention relates to a stabilizer mixture comprising a hindered amine light stabilizer, a triphenyl ketone UV absorber, and a diphenyl ketone UV absorber; a composition comprising an organic material, preferably an organic polymer, having undergone degradation induced by light, heat, oxidation, or agricultural chemical compounds; an article made from the composition, preferably a greenhouse film covering; and a method for stabilizing the aforementioned organic material.

[0002] More specifically, the present invention relates to a stabilizer mixture comprising components (a), (b) and (c), wherein component (a) is at least one compound of formula (A), wherein A1 is a C2-C18 alkyl, C5-C7 cycloalkyl, or C1-C4 alkyldi(C5-C7 cycloalkyl), group A2 is independently hydrogen, C1-C12 alkyl, C1-C12 alkoxy, C5-C12 cycloalkyl, or C5-C12 cycloalkoxy, A3 and A4 are independently hydrogen, C1-C12 alkyl, C5-C12 cycloalkyl, or a group of formula (a-1), or groups A3 and A4 together with the nitrogen atom to which they are bonded form a 5 to 10-membered heterocycle, and a is a value from 1 to 20 and the repeating units are the same or different; component (b) is at least one compound selected from formulas (B1) and (B-II), In this composition, E2, E3, E4, and E5 are independently hydrogen, C1-C18 alkyl, phenyl, or phenyl substituted with one, two, or three C1-C4 alkyl groups; n is 1 or 2; when n is 1, E1 is a C1-C18 alkyl or a C2-C18 hydroxyalkyl group intercalated with oxygen, and when n is 2, E1 is a bridging group of the formula -CH2CH2-OC(O)-(CH2)10-C(O)-O-CH2CH2-; Q1, Q2, Q3, and Q4 are independently hydrogen, C1-C18 alkyl, hydroxyl-substituted C1-C18 alkyl, or C2-C18 alkyl or a C2-C18 hydroxyalkyl group intercalated with oxygen; T1, T2, and T3 are independently hydrogen or C1-C18 alkyl; and component (c) is a compound of formula (C). Furthermore, the weight ratio of component (b) to (c) is 1:50 to 50:1.

[0003] Examples of alkyl groups having up to 18 carbon atoms are methyl, ethyl, propyl, isopropyl, n-butyl, dibutyl, 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-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, and octadecyl.

[0004] An example of an intercalated oxygen-containing C2-C18 hydroxyalkyl group is a group of the formula -CH2-CH(OH)-CH2-O-CH2-CH(C2H5)-(CH2)3-CH3.

[0005] Examples of C1-C12 alkoxy groups are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, and decoxy. C1-C8 alkoxy groups, specifically propoxy, are preferred.

[0006] Examples of C5-C12 cycloalkyl groups are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl.

[0007] Examples of C5-C12 cycloalkoxy groups are cyclopentoxy, cyclohexyloxy, cycloheptoxy, cyclooctoxy, cyclodecoxy, and cyclododecoxy. Cyclohexyloxy is preferred.

[0008] A preferred example of a phenyl group substituted with one, two or three C1-C4 alkyl groups is 2,4-dimethylphenyl.

[0009] Examples of C2-C18 alkyl groups are alkylene ethyl, alkylene propane, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene and hexamethylene.

[0010] An example of a C5-C7 cycloalkyl group is a cyclohexyl group.

[0011] An example of C1-C4 alkyl di(C5-C7 cycloalkyl) is methylene dicyclohexyl.

[0012] When groups A3 and A4 together with the nitrogen atom they are bonded to form a 5 to 10-membered heterocycle, the ring is, for example, 1-pyrrolidinyl, piperidinyl, 1-piperidyl, 4-methyl-1-piperidyl, 1-hexahydroazapyryl, 5,5,7-trimethyl-1-homoperidyl or 4,5,5,7-tetramethyl-1-homoperidyl.

[0013] In the compound of formula (A), the end group connected to the diamine residue is, for example, hydrogen or a group of the following formula, and the end group connected to the triamine is, for example, a group of formula or a group of formula.

[0014] A stabilizer mixture, wherein A1 is a C2-C18 alkyl, C5-C7 cycloalkyl or C1-C4 alkyldi(C5-C7 cycloalkyl), A2 is independently hydrogen, C1-C12 alkyl, C1-C12 alkoxy, C5-C12 cycloalkyl or C5-C12 cycloalkoxy, A3 and A4 are independently hydrogen, C1-C12 alkyl, C5-C12 cycloalkyl or a group of formula (a-1), and a is a value from 1 to 20 and the repeating units are the same or different.

[0015] A stabilizer mixture wherein A1 is a C2-C8 alkyl or cyclohexyl group, A2 is independently hydrogen, C1-C8 alkyl, C1-C12 alkoxy, cyclohexyl or cyclohexyloxy group, A3 and A4 are independently hydrogen, C1-C8 alkyl or a group of formula (a-1), and a is a value from 1 to 10, which is preferred.

[0016] A compound of formula (BI), wherein E2, E3, E4 and E5 are each independently hydrogen, C1-C4 alkyl or phenyl, is preferred. More preferably, n is 1 and E1 is C1-C10 alkyl.

[0017] A compound of formula (B-II), wherein Q1, Q2, Q3 and Q4 are each independently hydrogen or C1-C10 alkyl, and T1, T2 and T3 are each independently hydrogen or C1-C4 alkyl, is preferred.

[0018] Regarding component (b), compound of formula (BI) is preferred.

[0019] A compound of the following formula (A) is preferred: wherein one or two groups A2 are hydrogen and the remaining groups A2 are propoxy, wherein a is a value of 1 to 20, for example, 1 to 10, 2 to 20 or 2 to 10; wherein a is a value of 1 to 20, for example, 1 to 10, 2 to 20 or 2 to 10.

[0020] The following compounds are preferred for formulas (BI) and (B-II):

[0021] The compounds of formulas (B-1), (B-2) and (B-3) are preferred.

[0022] Most of the compounds of formula (A) and (B) are known and can be prepared by methods similar to those known to those skilled in the art.

[0023] The compound of formula (A) may be prepared, for example, by methods similar to those described in US-A-4,997,938, US-A-5,116,893, US-B-8,895,647, US-A-6,046,304, US-A-6117995, US-B-6420462 and US-B-6677451.

[0024] The compound of formula (B) can be prepared, for example, by a method similar to that described in US-B-6,255,483.

[0025] The compound of formula (C) is Chimassorb® 81, which is available from BASF SE.

[0026] The weight ratio of component (a) to (b) is 50:1 to 24:1, more preferably 45:1 to 24:1, even more preferably 40:1 to 24:1, and most preferably 37:1 to 24:1.

[0027] The weight ratio of components (b) to (c) is preferably 1:25 to 25:1, more preferably 1:25 to 5:1, and especially 1:25 to 1:1. An excellent ratio is 1:20 to 1:2, especially 1:15 to 1:2.

[0028] The weight ratio of component (a) to the total weight of components (b) and (c) is preferably 1:10 to 50:1, more preferably 1:5 to 50:1, and especially 1:2 to 40:1. The most preferred ratio is 1:2 to 40:1, and especially 1:1 to 40:1.

[0029] According to another embodiment, the weight ratio of component (a) to the total weight of components (b) and (c) is preferably 1:1 to 20:1.

[0030] The weight ratio of components (a) to (c) is preferably 1:10 to 40:1, more preferably 1:5 to 30:1, and especially 1:2 to 20:1. The most preferred ratio is 1:1 to 20:1, and especially 2:1 to 20:1.

[0031] According to another preferred embodiment, the stabilizer mixture further contains component (d), which is at least one compound selected from formulas (D-1) and (D-2). Wherein b is a value from 2 to 20.

[0032] The weight ratio of components (a) to (d) is preferably 20:1 to 1:1.

[0033] The weight ratio of the total weight of components (a) and (d) to the weight of component (b) is 50:1 to 24:1, more preferably 45:1 to 24:1, even more preferably 40:1 to 24:1, and most preferably 37:1 to 24:1.

[0034] In the compound of formula (D-2), depending on the preparation, the end group connected to oxygen is, for example, hydrogen and the end group connected to the -CO- group is, for example, -O-C1-C3 alkyl.

[0035] Another embodiment of the present invention is a composition comprising (I) an organic material, preferably an organic polymer, specifically a polyolefin, which undergoes degradation induced by light, heat, oxidation or agrochemical compounds and (II) a mixture of stabilizers as defined above.

[0036] An example of an organic material to be stabilized is...

[0037] 1. Polymers of monoolefins and dienes, such as polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, and polymers of cycloolefins, such as polymers of cyclopentene or norbornene, polyethylene (which may be crosslinked as appropriate), such as high-density polyethylene (HDPE), high-density and high-molecular-weight polyethylene (HDPE-HMW), high-density and ultra-high-molecular-weight polyethylene (HDPE-UHMW), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), (VLDPE) and (ULDPE).

[0038] Polyolefins (i.e., polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene) can be prepared by various methods, particularly by the following methods: a) group polymerization (usually carried out under high pressure and high temperature). b) catalytic polymerization, which uses a catalyst typically containing one or more metals from Groups IVb, Vb, VIb, or VIII of the periodic table. These metals typically have one or more ligands, usually oxides, halides, alcohols, esters, ethers, amines, alkyl, alkenyl, and / or aryl groups, which can be π-coordinated or σ-coordinated. These metal complexes can be in free form or immobilized on a matrix, typically on activated magnesium chloride, titanium(III) chloride, alumina, or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalyst itself can be used in the polymerization or other activators can be used, typically metal alkanes, metal hydrides, metal alkyl halides, metal alkyl oxides, or metal alkyl alkanes, where the metal is a Group Ia, IIa, or / or IIIa element of the periodic table. The activator can be suitably modified with other ester, ether, amine, or silicate ether groups. These catalyst systems are commonly referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene, or single-site catalysts (SSC).

[0039] 2.1) Mixtures of polymers mentioned below, such as mixtures of polypropylene and polyisobutylene, mixtures of polypropylene and polyethylene (e.g., PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (e.g., LDPE / HDPE).

[0040] 3. Copolymers of monoolefins and dienes with each other or with other vinyl monomers, such as ethylene / propylene copolymers, linear low-density polyethylene (LLDPE) and mixtures thereof with low-density polyethylene (LDPE), propylene / but-1-ene copolymers, propylene / isobutene 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, such as COC), ethylene / 1-olefin copolymers (wherein the 1-olefin is generated in situ); propylene / butadiene copolymers, isobutene / isoprene copolymers, ethylene / vinylcyclohexane copolymers Hexene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers or ethylene / acrylic acid copolymers and their salts (ionomers), and terpolymers of ethylene with propylene and dienes such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with each other and with polymers mentioned in 1) above, such as polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers (EVA), LDPE / ethylene-acrylic acid copolymers (EAA), LLDPE / EVA, LLDPE / EAA and alternating or random polyalkylene / carbon monoxide copolymers and mixtures with other polymers such as polyamide.

[0041] 4. Hydrocarbon resins (e.g., C5-C9), including their hydrogenation modification (e.g., tackifier) ​​and mixtures of polyalkylene and starch.

[0042] Homopolymers and copolymers from 1.) to 4.) may have any stereostructure including syndiotactic, isotactic, semi-isotactic or asteric; wherein asteric polymers are preferred. Stereoblock polymers are also included.

[0043] 5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

[0044] 6. Aromatic homopolymers and copolymers derived from vinyl aromatic monomers, including all isomers of styrene, α-methylstyrene, and vinyltoluene (especially p-vinyltoluene), all isomers of ethylstyrene, propylstyrene, vinylbiphenyl, vinylnaphthalene, and vinylanthracene, and mixtures thereof. Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, semi-isotactic, or atactic; atactic polymers are preferred. Stereoblock polymers are also included.

[0045] 6a. A copolymer comprising the aforementioned vinyl aromatic monomers and comonomers, selected from ethylene, propylene, diene, nitrile, acid, maleic anhydride, maleic diimide, vinyl acetate and vinyl chloride or acrylic acid derivatives and mixtures thereof, such as styrene / butadiene, styrene / acrylonitrile, styrene / ethylene (interpolymer), styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; a mixture of a styrene copolymer having high impact strength with another polymer, such as polyacrylate, diene polymer or ethylene / propylene / diene terpolymer; and block copolymers of styrene, such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butene / styrene or styrene / ethylene / propylene / styrene.

[0046] 6b. Hydrogenated aromatic polymers derived from the polymers mentioned under 6.) particularly include polycyclohexylethylene (PCHE) prepared by hydrogenation of non-standard polystyrene, commonly referred to as polyethylenecyclohexane (PVCH).

[0047] 6c. Hydrogenated aromatic polymers derived from the polymers mentioned under section 6a.)

[0048] Homopolymers and copolymers may have any stereostructure including syndiotactic, isotactic, semi-isotactic or anomalous; anomalous polymers are preferred. Stereoblock polymers are also included.

[0049] 7. Graft copolymers of vinyl aromatic monomers (such as styrene or α-methylstyrene), such as 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 maleic diimide on polybutadiene; styrene and maleic diimide on polybutadiene; styrene and alkyl acrylate or alkyl methacrylate on polybutadiene; styrene and acrylonitrile on ethylene / propylene / diene terpolymers; styrene and acrylonitrile on alkyl polyacrylate or alkyl polymethacrylate; styrene and acrylonitrile on acrylate / butadiene copolymers, and mixtures thereof with copolymers listed under 6), such as copolymers of polymers known to be ABS, MBS, ASA or AES.

[0050] 8. Halogenated polymers, such as polychloroprene, chlorinated rubber, chlorinated and brominated copolymers of isobutylene and isoprene (halobutyl rubber), chlorinated or sulfonated polyethylene, copolymers of ethylene and chlorinated vinyl, homopolymers and copolymers of epichlorohydrin, especially polymers containing halogenated vinyl compounds, such as polyvinyl chloride, polyvinylidene chloride, polyvinylidene fluoride, polyvinylidene fluoride and copolymers thereof, such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymers.

[0051] 9. Polymers derived from α,β-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates; polymethyl methacrylate, polyacrylamide and polyacrylonitrile, modified by butyl acrylate impact.

[0052] 10.9) The copolymers of the monomers mentioned below with each other or with other unsaturated monomers, such as acrylonitrile / butadiene copolymer, acrylonitrile / alkyl acrylate copolymer, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide copolymer or acrylonitrile / alkyl methacrylate / butadiene terpolymer.

[0053] 11. Polymers derived from unsaturated alcohols and amines or their acetal derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; and copolymers thereof with the olefins mentioned in item 1) above.

[0054] 12. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycol, polyethylene oxide, polypropylene oxide or copolymers thereof with diglycidyl ether.

[0055] 13. Polyacetal, such as polyoxymethylene and other polyoxymethylene containing ethylene oxide as a comonomer; polyacetal modified by thermoplastic polyurethane, acrylate or MBS.

[0056] 14. Polyphenylene ether and polyphenylene sulfide, and mixtures of polyphenylene ether with styrene polymers or polyamide.

[0057] 15. A polyether, polyester or polybutadiene, which is hydroxyl-terminated on the one hand, and a polyurethane derived from aliphatic or aromatic polyisocyanates and their precursors on the other hand.

[0058] 16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or corresponding endoramines, such as 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-xylenediamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic acid and / or terephthalic acid and having or not having an elastomer as a modifier. Examples include poly(2,4,4-trimethylhexamethylene terephthalamide) or poly(m-phenyl-m-phthalamide); block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers, or chemically bonded or grafted elastomers; or block copolymers with polyethers, such as block copolymers with polyethylene glycol, polypropylene glycol, or polybutylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide system).

[0059] 17. Polyurea, polyimide, polyamide-imide, polyetherimide, polyesterimide, polyvinylurea and polybenzimidazole.

[0060] 18. Polyesters derived from dicarboxylic acids and diols and / or hydroxycarboxylic acids or their corresponding lactones or lactides, such as poly(ethylene terephthalate), poly(butyl terephthalate), poly(1,4-dimethylolcyclohexane terephthalate), poly(alkyl naphthalene), and polyhydroxybenzoate, as well as copolyether esters derived from hydroxyl-terminated polyethers, and polyesters modified with polycarbonate or MBS. The copolyester may include, for example (but not limited to), poly(butyl succinate) / terephthalate, poly(butyl adipate) / terephthalate, poly(tetramethylene adipate) / terephthalate, poly(butyl succinate) / adipate, poly(butyl succinate) / carbonate, poly(3-hydroxybutyrate) / octanoate copolymer, and poly(3-hydroxybutyrate) / hexanoate / decanoate terpolymer. In addition, aliphatic polyesters may include, for example (but not limited to) poly(hydroxyalkanoates), specifically poly(propiolactone), poly(butyrolactone), poly(pentylenelactone), poly(valerolactone) and poly(caprolactone), polyethyl succinate, polypropyl succinate, polybutyl succinate, polyhexyl succinate, polyethyl adipate, polypropyl adipate, polybutyl adipate, polyethyl oxalate, polypropyl oxalate, polybutyl oxalate, polyhexyl oxalate, polyethyl sebacate, polypropyl sebacate, polybutyl sebacate and polylactic acid (PLA), as well as corresponding polyesters modified with polycarbonate or MBS. The term "polylactic acid (PLA)" refers to a homopolymer of preferred poly-L-lactide and any blend or alloy thereof with other polymers; copolymers of lactic acid or lactide with other monomers such as hydroxy-carboxylic acids, such as glycolic acid, 3-hydroxy-butyric acid, 4-hydroxy-butyric acid, 4-hydroxy-valerate, 5-hydroxy-valerate, 6-hydroxy-hexanoic acid and their cyclic forms; the term "lactic acid" or "lactide" includes L-lactic acid, D-lactic acid, mixtures thereof and dimers thereof, namely L-lactide, D-lactide, mesolactide and any mixture thereof.

[0061] 19. Polycarbonate and polyester carbonate.

[0062] 20. Polyketone.

[0063] 21. Polyurethane, polyetherurethane and polyetherketone.

[0064] 22. Crosslinked polymers derived from aldehydes on the one hand and from phenols, ureas and melamine on the other hand, such as phenol / formaldehyde resin, urea / formaldehyde resin and melamine / formaldehyde resin.

[0065] 23. Dry and non-drying alkyd resins.

[0066] 24. Copolyesters of self-saturated and unsaturated dicarboxylic acids and polyols and unsaturated polyester resins derived from ethylene compounds as crosslinking agents, and their halogen-modified forms with low flammability.

[0067] 25. Crosslinkable acrylic resins derived from substituted acrylates, such as epoxy acrylates, urethane acrylates, or acrylic polyesters.

[0068] 26. Alkyd resins, polyester resins and acrylate resins that are crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.

[0069] 27. A crosslinked epoxy resin derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, such as a product of diglycidyl ethers of bisphenol A and bisphenol F, which is crosslinked with a known curing agent (such as an anhydride or amine) in the presence or absence of an accelerator.

[0070] 28. Natural polymers, such as cellulose, rubber, gelatin and their chemically modified homologous derivatives, such as cellulose acetate, cellulose propionate and cellulose butyrate, or cellulose ethers such as methylcellulose; and rosin and its derivatives.

[0071] 29. Blends (polymer blends) of the aforementioned polymers, such as PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylate, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC.

[0072] 30. Naturally occurring and synthetic organic materials, such as mineral oil, animal and vegetable fats, oils and waxes or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates), and mixtures of synthetic esters and mineral oils in any weight ratio, are commonly used as mixtures of spin compositions and aqueous emulsions of such materials.

[0073] 31. Aqueous emulsions of natural or synthetic rubber, such as natural latex or latex of carboxylated styrene / butadiene copolymer.

[0074] The organic material is preferably a polyolefin, preferably a polyolefin selected from the group consisting of: linear low-density polyethylene, low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-butyl acrylate copolymer and polypropylene homopolymer or copolymer.

[0075] The stabilizer mixture according to the present invention may be present in the organic material to be stabilized in an amount of 0.005% to 10% or 0.005% to 5%, specifically 0.01% to 2.5% or 0.05% to 2%, with respect to the weight of the organic material.

[0076] Individual fractions of the stabilizing agent mixture of the present invention may be added to the organic material to be stabilized either individually or mixed with each other. Such fractions may be added to the polymer before, during, or after polymerization or before or after cross-linking.

[0077] The stabilizing agent composition according to the present invention or individual components thereof may be incorporated into the organic material to be stabilized by known methods by subsequent evaporation solvents may be used, for example, before or during shaping or by applying a dissolved or dispersed stabilizer to the organic material. The stabilizer may be added to an organic material in the form of powder, granules or masterbatch containing such stabilizer in a concentration of, for example, 2.5 to 90% by weight, preferably 2.5 to 25% by weight.

[0078] An example of treating or transforming a material stable according to the present invention is: Injection blow molding, extrusion, blow molding, rotation molding, in-mold decoration (reverse injection), slush molding, injection molding, co-injection molding, forming, compression molding, pressing, film extrusion (cast film; blow molding film), fiber spinning (braided, non-braided) ), stretching (uniaxial, biaxial), bonding, deep drawing, calendering, mechanical transformation, sintering, co-extrusion, coating, lamination, cross-linking (radiation, peroxide, silane), gas-phase deposition, welding together, gluing, rubber vulcanization (vulkani zation), thermoforming, pipe extrusion, styling extrusion, sheet extrusion;sheet casting, spin coating, overlapping, foaming, recirculation / rework, extrusion coating, destick cracking (peroxide, thermal), fiber meltblown, spinning, surface treatment (electrical dizziness discharge, flame, plasma), sterilization (via γ rays, electron beams), casting polymerization (R&M treatment, RAM extrusion), gel coating, strip extrusion, GMT treatment, SMC treatment, plastic sol and dip coating (PVC, latex).

[0079] The stabilized material may additionally also contain various known additives, such as: 1. Antioxidants

[0080] 1.1. Alkylated monophenols, such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-acetol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-di(octadecyl)-4-methyl Phenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol; nonylphenols with straight or branched side chains, such as 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'-methyltetadecadec-1'-yl)phenol and mixtures thereof.

[0081] 1.2. Alkylthiomethylphenol, such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-acetol, 2,6-di-dodecylthiomethyl-4-nonylphenol.

[0082] 1.3. Hydroquinone and alkylated hydroquinone, such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-pentylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxymethoxybenzene, 3,5-di-tert-butyl-4-hydroxymethoxybenzene, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, and bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipic acid.

[0083] 1.4. Tocopherols, such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).

[0084] 1.5. Hydroxylated thiodiphenyl ethers, such as 2,2'-thiobis(6-tertiary butyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tertiary butyl-3-methylphenol), 4,4'-thiobis(6-tertiary butyl-2-methylphenol), 4,4'-thiobis(3,6-di-secondary pentylphenol), and 4,4'-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide.

[0085] 1.6. Alkylene bisphenols, such as 2,2'-methylenebis(6-tri-butyl-4-methylphenol), 2,2'-methylenebis(6-tri-butyl-4-acetol), 2,2'-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol], 2,2'-methylenebis(4-methyl-6-cyclohexylphenol), 2,2'-methylenebis(6-nonyl-4-methylphenol), 2,2'-methylenebis(4,6-di-tri-butylphenol), 2,2'- Ethylenebis(4,6-di-tertiary butylphenol), 2,2'-ethylenebis(6-tertiary butyl-4-isobutylphenol), 2,2'-methylenebis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-methylenebis(2,6-di-tertiary butylphenol), 4,4'-methylenebis(6-tertiary butyl-2-methylphenol), 1,1-bis(5-tertiary butyl-4- Hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxyphenylmethyl)-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-dodecyl mercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentane Diene, bis[2-(3'-tert-butyl-2'-hydroxy-5'-tolylmethyl)-6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis-(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-bis-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

[0086] 1.7. O-benzyl compounds, N-benzyl compounds and S-benzyl compounds, such as 3,5,3',5'-tetra-tert-butyl-4,4'-dihydroxydiphenylmethyl ether, octadecyl-4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5-di-tert-butyl-4-hydroxybenzyl mercaptoacetate.

[0087] 1.8. Hydroxyphenylmethylated malonate, such as di(octadecyl)-2,2-bis(3,5-di-tertiary butyl-2-hydroxyphenylmethyl)malonate, di-octadecyl-2-(3-tertiary butyl-4-hydroxy-5-methylphenylmethyl)malonate, di-dodecyl mercaptoethyl-2,2-bis(3,5-di-tertiary butyl-4-hydroxyphenylmethyl)malonate, bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tertiary butyl-4-hydroxyphenylmethyl)malonate.

[0088] 1.9. Aromatic hydroxybenzenemethyl compounds, such as 1,3,5-trimethylbenzene (3,5-di-tert-butyl-4-hydroxybenzene)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzene)-2,3,5,6-tetramethylbenzene, and 2,4,6-trimethylbenzene (3,5-di-tert-butyl-4-hydroxybenzene)phenol.

[0089] 1.10. Triple compounds, such as 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyaniline)-1,3,5-triple, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyaniline)-1,3,5-triple, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triple, 2,4,6-triple (3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3- Trisodium, 1,3,5-tris(3,5-di-tertiary butyl-4-hydroxyphenylmethyl) isocyanurate, 1,3,5-tris(4-tertiary butyl-3-hydroxy-2,6-dimethylphenylmethyl) isocyanurate, 2,4,6-tris(3,5-di-tertiary butyl-4-hydroxyphenylethyl)-1,3,5-trisodium, 1,3,5-tris(3,5-di-tertiary butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-trisodium and 1,3,5-tris(3,5-dicyclohexyl-4-hydroxyphenylmethyl) isocyanurate.

[0090] 1.11. Benzyl phosphonates, such as calcium salts of monoethyl esters of dimethyl-2,5-di-tri-butyl-4-hydroxybenzyl phosphonate, diethyl-3,5-di-tri-butyl-4-hydroxybenzyl phosphonate, di(octadecyl)3,5-di-tri-butyl-4-hydroxybenzyl phosphonate, di(octadecyl)-5-tri-butyl-4-hydroxy-3-methylbenzyl phosphonate, and 3,5-di-tri-butyl-4-hydroxybenzyl phosphonic acid.

[0091] 1.12. Acrylaminophenols, such as 4-hydroxydodecylaminobenzene, 4-hydroxyoctadecylaminobenzene, and N-(3,5-di-tert-butyl-4-hydroxyphenyl)aminocarbamate octyl ester.

[0092] 1.13. β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with the following esters: monools or polyols, such as methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, neopentyltetrol, s(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxadiazine, 3-thiadecyl alcohol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0093] 1.14. β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid esters with the following: monools or polyols, such as methanol, ethanol, n-octanol, isooctanol, stearyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, diethylene glycol, triethylene glycol, neopentyl tertrol, senna (hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl) oxalate Acetylamine, 3-thiadecyl alcohol, 3-thiadecyl alcohol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane; 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0094] 1.15. β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with the following esters: monools or polyols, such as methanol, ethanol, octanol, stearyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, neopentyltetrol, s(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxadiazine, 3-thiadecyl alcohol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0095] 1.16.3,5-Di-tert-butyl-4-hydroxyphenylacetic acid with the following esters: monools or polyols, such as methanol, ethanol, octanol, stearyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, neopentyl tertrol, s(hydroxyethyl) isocyanurate, N,N′-bis(hydroxyethyl) glyphosate, 3-thiadecyl alcohol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0096] 1.17. Acrylates of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, such as N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionic acid)hexamethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionic acid)trimethylenediamine, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionic acid)acehydrazine, N,N'-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propoxy)ethyl]oxadiamine (Naugard® XL-1, supplied by Uniroyal).

[0097] 1.18. Ascorbic acid (vitamin C)

[0098] 1.19. Amine antioxidants, such as N,N'-di-isopropyl-p-phenylenediamine, N,N'-di-di-secondary-butyl-p-phenylenediamine, N,N'-bis(1,4-dimethylpentyl)-p-phenylenediamine, N,N'-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine, N,N'-bis(1-methylheptyl)-p-phenylenediamine, N,N'-dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl- p-Phenylenediamine, N-(1-methylheptyl)-N'-phenyl-p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4-(p-toluidinesulfonyl)diphenylamine, N,N'-dimethyl-N,N'-di-secondary butyl-p-phenylenediamine, diphenylamine, N-allyl diphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tertiary octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, such as p,p'-di-tertiary octyl diphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonyrylaminophenol, 4-dodecyl Aminophenol, 4-octadecylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(aniline)propane, (o-tolyl)biguanidine, bis[4-(1',3'-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, monoalkylated and dialkylated tert-butyl / tert-octyldiphenyl Mixtures of amines, mixtures of monoalkylated and dialkylated nonyldiphenylamine, mixtures of monoalkylated and dialkylated dodecyldiphenylamine, mixtures of monoalkylated and dialkylated isopropyl / isohexyldiphenylamine, mixtures of monoalkylated and dialkylated tributyldiphenylamine, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazoline, phenoxythiazoline, mixtures of monoalkylated and dialkylated tributyl / trimethyloctylphenoxythiazoline, mixtures of monoalkylated and dialkylated trimethyloctylphenoxythiazoline, N-allylphenoxythiazoline, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene.

[0099] 2. UV absorbers and light stabilizers

[0100] 2.1. 2-(2'-hydroxyphenyl)benzotriazole, such as 2-(2'-hydroxy-5'-methylphenyl)-benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5 -Chloro-benzotriazole, 2-(3'-secondary butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-(3',5'-di-tert-pentyl-2'-hydroxyphenyl)benzotriazole, 2-(3',5'-bis-(α,α-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl-5'-[2] -(2-ethylhexyloxy)-carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl)benzotriazole ]-2'-hydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2-ylphenol]; transesterification products of 2-[3'-tert-butyl-5'-(2-methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300; wherein R = 3'-tert-butyl-4'-hydroxy-5'-2H-benzotriazole-2-ylphenyl, 2-[2'-hydroxy-3'-(α,α-dimethylbenzyl)-5'-(1,1,3,3-tetramethylbutyl)-phenyl]benzotriazole; 2-[2'-hydroxy-3'-(1,1,3,3-tetramethylbutyl)-5'-(α,α-dimethylbenzyl)-phenyl]benzotriazole.

[0101] 2.2. 2-Hydroxydiphenyl ketone, such as 4-hydroxy, 4-methoxy, 4-decoxy, 4-dodecoxy, 4-benzoxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.

[0102] 2.3. Esters of substituted and unsubstituted benzoic acids, such as 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoic acid, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoic acid, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoic acid, and 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoic acid.

[0103] 2.4. Acrylates, such as ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate, methyl α-methoxycarbonylcinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxy-cinnamate, methyl α-methoxycarbonyl-p-methoxycinnamate, N-(β-methoxycarbonyl-β-cyanovinyl)-2-methylindoline, tetrakis(α-cyano-β,β-diphenylacrylate neopentyl ester).

[0104] 2.5. Nickel compounds, such as nickel complexes of 2,2'-thio-bis[4-(1,1,3,3-tetramethylbutyl)phenol], such as 1:1 or 1:2 complexes, with or without additional ligands, such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine; nickel dibutyldithiocarbamate; nickel salts of monoalkyl esters (e.g. methyl or ethyl) of 4-hydroxy-3,5-bis-tert-butylbenzylphosphonic acid; nickel complexes of ketoximes (e.g. 2-hydroxy-4-methylphenylundecyl ketoxime); nickel complexes of 1-phenyl-4-dodecyl-5-hydroxypyrazole, with or without additional ligands.

[0105] 2.6. Stericly hindered amines, such as bis(1-undecoxy-2,2,6,6-tetramethyl-4-piperidinyl) carbonate, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidinyl) succinate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, bis(1-octoxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, n-butyl-3,5-bis-tert-butyl-4-hydroxybenzylmalonic acid bis(1,2,2,6,6-pentamethyl-4-piperidinyl) ester, condensates of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, N, Linear or cyclic condensates of N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexanediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, triazine (2,2,6,6-tetramethyl-4-piperidinyl)azonotriacetate, tetra(2,2,6,6-tetramethyl-4-piperidinyl)-1,2,3,4-butanetetracarboxylate, 1,1'-(1,2-ethanediyl)-bis(3,3,5,5-tetramethylpiperidone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidinyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butyl) 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, bis(1-octoxy-2,2,6,6-tetramethylpiperidinyl)succinate, bis(1-octoxy-2,2,6,6-tetramethylpiperidinyl)succinate, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine and 4-morpholinyl-2,6-dichloro-1,3,5-triazine condensates, 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidinyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane condensates, 2-chloro-4,6-di-(4 - n-Butylamino-1,2,2,6,6-pentamethylpiperidinyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane condensate, 8-acetylated-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidinyl)pyrrolidin-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidinyl)pyrrolidin-2,5-dione, a mixture of 4-hexadecoxy-2,2,6,6-tetramethylpiperidine and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, N,N'-bis(2,2,6,The condensate of 6-tetramethyl-4-piperidinyl)hexanediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-tris(II), the condensate of 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-tris(II) and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Registry No. [136504-96-6]); the condensate of 1,6-hexanediamine and 2,4,6-trichloro-1,3,5-tris(II), N,N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpiperidine (C AS Registry No. [192268-64-7]); N-(2,2,6,6-tetramethyl-4-piperidinyl)-n-dodecylbutadieneimide, N-(1,2,2,6,6-pentamethyl-4-piperidinyl)-n-dodecylbutadieneimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-sideoxy-spiro[4,5]decane, 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-sideoxy-spiro[4,5]decane and the table The reaction products of chlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidinyloxycarbonyl)-2-(4-methoxyphenyl)ethylene, N,N'-bis-methacryl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexanediamine, diester of 4-methoxymethylenemalonic acid and 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidinyl)]siloxane, maleic anhydride α-olefin copolymer and 2,2 The reaction products of 6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine, 2,4-bis[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-N-butylamino]-6-(2-hydroxyethyl)amino-1,3,5-trimethylolamine, 1-(2-hydroxy-2-methylpropoxy)-4-octadecyloxy-2,2,6,6-tetramethylpiperidine, 5-(2-ethylhexyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, Sanduvor [Clariant; CAS Registry No. 106917-31-1], 5-(2-ethylhexyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl)butylamino]-6-chloro-s-triamine and N,N'-bis(3-aminopropyl)ethylenediamine), 1,3,5-tris(N-cyclohexyl-N-(2,2,6,6-tetramethylpiperidin-3-one-4-yl)amino)-s-triamine, 1,3,5-tris(N-cyclohexyl-N-(1,2,2,6,6-pentamethylpiperidin-3-one-4-yl)amino)-s-triamine,

[0106] 2.7. Glycerylamines, such as 4,4'-dioctyloxyglycerylaniline, 2,2'-diethoxyglycerylaniline, 2,2'-dioctyloxy-5,5'-di-tert-butyroxycerylaniline, 2,2'-di(dodecyloxy)-5,5'-di-tert-butyroxycerylaniline, 2-ethoxy-2'-ethylglycerylaniline, N,N'-bis(3- (-Dimethylaminopropyl) oxadiazine, 2-ethoxy-5-tert-butyl-2'-acetazine and mixtures thereof with 2-ethoxy-2'-ethyl-5,4'-bis-tert-butyl-acetazine, mixtures thereof with p-methoxy-disubstituted oxadiazine and mixtures thereof with p-ethoxy-disubstituted oxadiazine.

[0107] 2.8. 2-(2-hydroxyphenyl)-1,3,5-triphenyl, for example 2,4,6-triphenyl(2-hydroxy-4-octoxyphenyl)-1,3,5-triphenyl, 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triphenyl, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triphenyl, 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triphenyl, 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(4-methylphenyl) -1,3,5-trisyl, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-trisyl, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-trisyl, 2-[2-hydroxy-4-(2-hydroxy-3-butoxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-trisyl, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-trisyl, 2- [4-(dodecyloxy / tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triphenyl, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triphenyl, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triphenyl, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triphenyl, 2,4,6-triphenyl[2-hydroxy-4-(3-butoxy-2-hydroxyphenyl)-4,6-diphenyl-1,3,5-triphenyl] [Propoxy)phenyl]-1,3,5-triphenyl, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triphenyl, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropoxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triphenyl, 2,4-bis(4-[2-ethylhexyloxy]-2-hydroxyphenyl)-6-(4-methoxyphenyl)-1,3,5-triphenyl, 2,4-bis(4-biphenyl)-6-[2-hydroxy-4-(2-ethylhexyloxy)phenyl]-1,3,5-triphenyl.

[0108] 3. Metal deactivators, such as N,N'-diphenylglyoxalamine, N-salicylicalaldehyde-N'-salicylichydrazine, N,N'-bis(salicylic)hydrazine, N,N'-bis(3,5-di-tri-butyl-4-hydroxyphenylpropionic)hydrazine, 3-salicylicamine-1,2,4-triazole, bis(benzylmethyl)glyoxalidin, glyoxalaniline, isophthalamide dihydrazine, sebadiylbisphenylhydrazine, N,N'-diacetylatedhexadihydrazine, N,N'-bis(salicylic)glyoxalidin, N,N'-bis(salicylic)thiopropionic dihydrazine.

[0109] 4. Phosphites and phosphonates, such as triphenyl phosphite, diphenylalkyl phosphite, phenyl dialkyl phosphite, nonylphenyl phosphite, dodecyl phosphite, octadecyl phosphite, distearate neopentyltetrol diphosphite, 2,4-di-tert-butylphenyl phosphite, diisodecylneopentyltetrol diphosphite, bis(2,4-di-tert-butylphenyl)neopentyltetrol diphosphite, bis(2,4-di-isopropylphenyl ... Pentylenetetroxide diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)neopentylenetetroxide diphosphite, diisodecoxyneopentylenetetroxide diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)neopentylenetetroxide diphosphite, bis(2,4,6-tris(tert-butylphenyl)neopentylenetetroxide diphosphite, tristearylsorbitol triphosphite, tetra(2,4-di-tert-butylphenyl)4,4'-epimine diphosphite, 6-isooctyloxy-2,4 8,10-Tetra-tertiary butyl-12H-dibenzo[d,g]-1,3,2-dioxophosphorus octacyclopenta ... [Tetra-tertiary butyl-1,1'-biphenyl-2,2'-diyl) phosphite], 2-ethylhexyl(3,3',5,5'-tetra-tertiary butyl-1,1'-biphenyl-2,2'-diyl) phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tertiary butylphenoxy)-1,3,2-dioxaphosphacyclopropane, a mixed triphosphite of 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl (CAS: 939402-02-5), triphenyl phosphite, polymers having α-hydro-ω-hydroxy poly[oxy(methyl-1,2-ethanediyl)], C10-16-alkyl esters (CAS: 1227937-46-3).

[0110] The following phosphites are particularly preferred: phosphite tannin (2,4-di-tri-butylphenyl ester) (Irgafos®168, Ciba Specialty Chemicals Inc.), phosphite tannin (nonylphenyl ester).

[0111] 5. Hydroxylamine, such as N,N-diphenylmethylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-di(dodecyl)hydroxylamine, N,N-di(tetradecyl)hydroxylamine, N,N-di(hexadecyl)hydroxylamine, N,N-di(octadecyl)hydroxylamine, N-hexadecyl-N-octadecyl hydroxylamine, N-heptadecyl-N-octadecyl hydroxylamine, and N,N-dialkyl hydroxylamine, which are derived from hydrogenated animal lipamines.

[0112] 6. Nitroketones, such as N-benzyl-α-phenyl nitrone, N-ethyl-α-methyl nitrone, N-octyl-α-heptyl nitrone, N-dodecyl-α-undecyl nitrone, N-tetradecyl-α-tetrazyl nitrone, N-hexadecyl-α-pentadecanyl nitrone, N-octadecyl-α-heptadecyl nitrone, N-hexadecyl-α-heptadecyl nitrone, N-octadecyl-α-pentadecanyl nitrone, N-octadecyl-α-heptadecyl nitrone, and nitrones derived from N,N-dialkylhydroxylamine.

[0113] 7. Thio synergists, such as di(dodecyl) thiodipropionate, dimystryl thiodipropionate, distearate, or distearate disulfide.

[0114] 8. Peroxide scavengers, such as esters of β-thiodipropionic acid, such as dodecyl ester, stearyl ester, myristyl ester or tridecyl ester, zinc salts of mercaptobenzimidazole or 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, di(octadecyl)disulfide, neopentyltetroxide(β-dodecylmercapto)propionate.

[0115] 9. Polyamide stabilizers, such as copper salts and divalent manganese salts in combination with iodides and / or phosphorus compounds.

[0116] 10. Alkaline co-stabilizers, such as melamine, polyvinylpyrrolidone, dicyandiamine, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, such as calcium stearate, zinc stearate, magnesium betaine, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony catechol and zinc catechol.

[0117] 11. Nucleating agents, such as inorganic substances, like talc; metal oxides, such as titanium dioxide or magnesium oxide, preferably phosphates, carbonates or sulfates of alkaline earth metals; organic compounds, such as monocarboxylic acids or polycarboxylic acids and their salts, such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds, such as ionic copolymers (ionomers). Preferably, 1,3:2,4-bis(3',4'-dimethylbenzylmethylene)sorbitol, 1,3:2,4-bis(p-methyldiphenylmethylene)sorbitol and 1,3:2,4-bis(benzylmethylene)sorbitol.

[0118] 12. Fillers and reinforcing agents, such as calcium carbonate, silicates, surface-treated silica (as described, for example, in US-A-2007 / 60,697 and US-A-2009 / 111,918), glass fibers, glass beads, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flour or other natural product fibers, and synthetic fibers.

[0119] 13. Other additives, such as plasticizers, lubricants, emulsifiers, pigments, rheology modifiers, catalysts, flow control agents, optical brighteners, flame retardants, antistatic agents and foaming agents.

[0120] 14. Benzofuranones and indololinones, for example disclosed in US 4,325,863; US 4,338,244; US 5,175,312; US 5,216,052; US 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839, EP-A-0591102; EP-A-1291384, or 3-[4-(2-ethoxyethoxy)phenyl]-5,7-di-tri-butylbenzofuran-2-one, 5,7-di-tri-butyl-3-[4-(2-stearyloxyethoxy)phenyl]benzofuran-2-one, 3,3' -Bis[5,7-di-tertiary butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tertiary butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-ethoxy-3,5-dimethylphenyl)-5,7-di-tertiary butylbenzofuran-2-one, 3-(3,5-dimethyl-4-pentacyclooxyphenyl)-5,7-di-tertiary butylbenzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tertiary butylbenzofuran-2-one, 3-(2,3-dimethylphenyl)-5,7-di-tertiary butylbenzofuran-2-one, 3-(2-ethoxy-5-isooctylphenyl)-5-isooctylbenzofuran-2-one.

[0121] The weight ratio of the total amount of the stabilizer mixture of the present invention to the total amount of conventional additives can be, for example, 100:1 to 1:1000, or 10:1 to 1:100, or 20:1 to 1:20, or 10:1 to 1:10.

[0122] Another embodiment of the present invention is a composition that further contains another additive selected from the group consisting of: antioxidants, slip agents, anti-sticking agents, heat fillers, pigments, anti-fogging agents and anti-hazing agents.

[0123] The material stable according to the present invention can be used in a variety of forms, such as in the form of film, fiber, tape, molding composition, profile or adhesive for paint, adhesive or putty.

[0124] More specifically, the stable material according to the present invention can be used to manufacture the following devices: I-1) Automotive applications, specifically shock absorbers, dashboards, battery packs, rear and front linings, under-hood model parts, roof boxes, trunk linings, interior linings, airbag covers, electronic molded parts for accessories (lights), dashboard bezels, headlight glass, instrument panels, exterior linings, interior trim, automotive lights, headlights, parking lights, taillights, brake lights, interior and exterior trim panels; door panels; fuel tanks; front glass; rear windows; seat backs, exterior panels, wire insulation, profile extrusions for sealing, cladding, pillar covers, chassis components, exhaust systems, fuel filters / fillers, fuel pumps, fuel tanks, body side moldings, rub strips, convertible roofs, exterior mirrors, exterior trim panels, fasteners / fixtures, front-end modules, glass, hinges, locking systems, luggage / roof racks. racks), press / stamping components, seals, side impact protection components, mufflers / soundproofing devices, and sunroofs.

[0125] I-2) Devices used in aircraft, railways, motor vehicles (cars, motorcycles) (including furnishings).

[0126] I-3) Devices used in space applications (specifically rockets and satellites), such as reentry protection components.

[0127] I-4) Devices used in architecture and design, mining applications, noise reduction systems, street shelters and refuges.

[0128] II-1) Electrical equipment, specifically washing machines, drums, dryers (microwave dryers), dishwashers, blenders and irons.

[0129] II-2) Foil used for encapsulation of capacitors, refrigerators, heating devices, air conditioners, electronic devices, semiconductors, coffee machines and vacuum cleaners.

[0130] III-1) Technical articles, such as gears, sliding parts, spacers, screws, handles and knobs.

[0131] III-2) Rotor blades, fan and windmill blades, solar energy devices, swimming pools, pool covers, pool linings, water tank linings, closets, wardrobes, partition walls, panel walls, folding walls, roofs, louvers (e.g., roller blinds), fittings, pipes, sleeves and connectors between conveyor belts.

[0132] III-3) Any geometric structure (window glass panel) and panel profile.

[0133] III-4) Glass alternatives, specifically extruded sheets, for use in buildings (monolithic, double or multi-layer), aircraft, schools, extruded sheet glass, for use in architectural glass, trains, transportation, hygiene products and greenhouse window films.

[0134] III-5) Boards (walls, cutting boards), extrusion coatings (photosensitive paper, corner wraps and pipe coatings), silos, wood substitutes, plastic sheets, wood composites, walls, surfaces, furniture, decorative foils, floor coverings (internal and external applications), flooring, movable flooring and tiles.

[0135] III-6) Applications of cement, concrete, composite materials and coverings, paneling and cladding, handrails, railings, kitchen countertops, roofs, roofing panels, ceramic tiles and waterproof fabrics.

[0136] IV-1) Boards (walls and cutting boards), trays, artificial turf, astroturf, artificial coverings for stadium tracks (athletics), artificial flooring and tape for stadium tracks (athletics).

[0137] V-1) Plastic film, generally speaking (packaging, transshipment, lamination, pool covers, garbage bags, wallpaper, shrink film, raffia fiber, desalination film, battery packs and connectors).

[0138] V-2) Agricultural films (greenhouse coverings, tunnels, mulches, silage, bundled packaging), especially in the presence of intensive agrochemical applications.

[0139] VI-1) Food packaging and covering materials (flexible and solid), BOPP, BOPET, bottles.

[0140] VI-2) Filter cartridges, syringes, medical applications, containers for any transport, waste baskets and bins, waste bags, boxes, garbage bins, garbage bags, wheeled boxes, general containers, tanks for water / use of water / chemicals / gases / oil / gasoline / diesel; tank liners, boxes, crates, battery casings, grooves, medical devices such as pistons, ophthalmic applications, diagnostic devices and pharmaceutical bubble wrap.

[0141] VII-1) An apparatus for filling polymers (talc, chalk, kaolin, silash, pigments, carbon black, TiO2, mica, nanocomposite, dolomite, silica, silicates, glass, asbestos).

[0142] Therefore, another embodiment of the present invention is an article made from the composition described above. Plastic articles (preferably films) for agricultural use, typically obtained by blow molding extrusion technology, are preferred. Particular interest is focused on single-layer films or multilayer films of 60 to 100 micrometers, typically with a thickness of 180 micrometers or 120 micrometers. The most important application of thin plastic films in agriculture is as coverings for greenhouses and tunnels to grow crops in protected environments.

[0143] It is also preferred to be a multilayer film, more preferably a multilayer polyolefin film, specifically a multilayer polyethylene film, which contains a compound of formula (A) in at least one layer and a compound of formula (B) in another layer.

[0144] This multilayer film is typically made of three, five, or seven layers. This can produce film structures such as: ABA, ABC, ABCBA, ABCBD, ABCDCBA, or AABCBAA. A, B, C, and D represent the different polymers and thickeners mentioned below.

[0145] However, adjacent layers may also be coupled so that the final membrane article can be made of an even number of layers, i.e. two, four or six layers, such as AABA, AABB, AABAA, ABBAA, AABCB, AABCAA and the like.

[0146] Films containing one of the aforementioned light stabilizers are typically made of low-density polyethylene (from group-polymerized or linear types), linear low-density polyethylene, metallocene linear low-density polyethylene, C4-LLDPE, C8-LLDPE, medium-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-butyl acrylate copolymer, ethylene-methyl acrylate copolymer, and combinations thereof, made of polypropylene (homogeneous and copolymeric) or made of high-density polyethylene. This may include multiple layers of the same polymer type with different viscosities or comonomer contents (e.g., vinyl acetate content) or virgin polymers and re-grinding or recycled materials. This may include strength layers of polyamide 6 and polyamide 6.6, or connecting layers of polyisobutylene, maleic anhydride-grafted polyethylene, maleic anhydride-grafted polypropylene, or biodegradable resin layers. Such combinations are optimized to, for example, maximize the initial mechanical properties of plastic products (tensile strength, puncture resistance, impact resistance, elongation), improve interlayer adhesion strength, or achieve their special functions (gas barrier properties, transparency, heat seal properties).

[0147] The stabilizer mixture according to the invention is particularly suitable for stabilizing greenhouse film coverings that come into contact with agricultural chemical compounds, such as Metam-Sodium (N-methyldithiocarbamate), Cymoxanil (2-cyano-N-[(ethylamino)carbonyl]-2-(methoxyimino)acetamide), Thiram (bis(dimethylaminothiomethyl)disulfide), Mancozeb (Mn-Zn-ethylbis(dithiocarbamate)) or elemental sulfur, specifically elemental sulfur or Metam-Sodium.

[0148] Therefore, another embodiment of the present invention is a greenhouse film covering that comes into contact with agricultural chemical compounds.

[0149] Another embodiment of the present invention is a method for stabilizing organic materials, preferably organic polymers, to resist degradation induced by light, heat, oxidation or agrochemical compounds, comprising incorporating a mixture of stabilizers as defined above into the organic material.

[0150] The following examples illustrate the invention in more detail. Unless otherwise stated, all percentages and parts are by weight. Example:

[0151] The stabilizers are listed in Tables 1 to 4 below: Compound (A-3-1): where a is a value from 1 to 10. Compound (A-4-1): where a is a value from 1 to 10. Compound (B-1): Compound (B-2): Compound (B-3): Compound (C): Compound (D-1): Compound (D-2): (Tinuvin® 622) where b is a value from 2 to 10. Application Examples 1 to 7 A) Preparation of membrane samples:

[0152] Stability of LDPE (Low-Density Polyethylene) Multilayer Films: A formulation containing the following components was prepared: LDPE powder (Polimeri Europa Riblene® FC 30, characterized by a density of 0.922 g / cm³ and a melt flow index (190°C / 2.16 kg) of 0.27 g / 10 min), 0.04 wt% of 2,4-di-tert-butylphenyl phosphite relative to the weight of LDPE, 0.01 wt% of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate relative to the weight of LDPE, and a mixture of stabilizers indicated in Tables 1 and 2. The formulations were mixed in a turbo mixer. Each formulation was extruded in a laboratory-scale single-screw Collin extruder (Ø 42 mm, L / D = 25) at a maximum temperature of 200°C. Next, each final formulation was blow-molded in a laboratory-scale Collin® 5-layer blow extruder (Ø 20-25-30 mm, L / D 25) at a maximum temperature of 210°C to obtain a 5-layer film with the same formulation in all layers. The total film thickness was 160 μm (50 μm - 15 μm - 30 μm - 15 μm - 50 μm). B) Test Methods

[0153] The prepared films were subjected to agrochemical treatment prior to artificial weathering. Film specimens of each formulation were mounted in a small experimental greenhouse (geographic coordinates: 44°25'40"N, 11°16'39"E) equipped with two burners of the type commonly used in agricultural practice to allow the sublimation of elemental sulfur (a widely used fungicide). So-called "sulfur combustion" was conducted for 13 consecutive days, 6 hours per day, while the films were mounted in the small experimental greenhouse. The film specimens were covered with an additional single-piece opaque film to minimize direct exposure to sunlight, thereby minimizing the effects of sunlight and potential variability in the exposure of samples in subsequent test series. The amount of sulfur burned was adjusted and weathering conditions were closely monitored to obtain the desired level of sulfur contamination in the film samples, which was measured by inductively coupled plasma.

[0154] Following agrochemical treatment, membrane samples of each formulation were exposed to an Atlas Weather-O-Meter (WOM, according to ASTM G155, 0.35 W / m² at 340 nm, dry cycle) to accelerate photoweathering. Following exposure, membrane samples were obtained at defined time intervals and subjected to tensile testing. Residual tensile strength was measured using a Zwick® Z1.0 constant-velocity tensile meter (according to modified ISO 527) to assess the degradation of mechanical properties of the membrane samples due to polymer degradation following oxidation.

[0155] The test results are listed in Tables 1 and 2 below. Table 1: Membrane samples were contaminated with sulfur content of up to 5000 ppm and exposed to WOM. Stabilizer mixture (by weight of polymer composition) Elongation at break (in initial %) after 4000 hours of WOM treatment Example 1 (Comparative) 0.550% of compound (A-4-1) 0.064% of compound (C) 6.4 Example 2 0.550% of compound (A-4-1) 0.015% of compound (B-1) 0.049% of compound (C) 77.1 Example 3 0.550% of compound (A-4-1) 0.015% of compound (B-2) 0.049% of compound (C) 78.9 Example 4 0.550% of compound (A-4-1) 0.015% of compound (B-3) 0.049% of compound (C) 69.4 Higher values ​​are appropriate. Table 2: Membrane samples contaminated with sulfur content up to 5000 ppm and exposed to WOM. Stabilizer mixture (by weight of polymer composition) Elongation at break (in initial %) after 4000 hours of WOM treatment Example 5 (Comparative) 0.350% of compound (A-4-1) 0.050% of compound (D-1) 0.150% of compound (D-2) 0.064% of compound (C) 61.8 Example 6 0.350% of compound (A-4-1) 0.050% of compound (D-1) 0.150% of compound (D-2) 0.049% of compound (C) Compound (B-1) at 0.015 88.2 Example 7 0.350% of compound (A-4-1) 0.050% of compound (D-1) 0.150% of compound (D-2) 0.049% of compound (C) Compound (B-3) at 0.015 79.7 A higher value is appropriate. Examples 8 to 11, Application A): Preparation of membrane samples:

[0156] Preparation of stabilized LDPE (low-density polyethylene) / LLDPE (linear low-density polyethylene) / EVA (ethylene-vinyl acetate copolymer) multilayer film samples: Concentrated formulations containing the following were prepared: a total of 20% of the stabilizer mixtures indicated in Tables 3 and 4 below, LDPE powder (Polimeri Europa Riblene® FC 30, characterized by a density of 0.922 g / cm³ and a melt flow index (190°C / 2.16 kg) of 0.27 g / 10 min), 0.04 wt% of phosphite {2,4-di-tert-butylphenyl ester} relative to the weight of LDPE, and 0.01 wt% of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate relative to the weight of LDPE. The formulations were mixed in a turbo mixer. Each formulation was extruded in a laboratory-scale twin-screw Comac extruder (Ø 34 mm, L / D = 32) at a maximum temperature of 200°C. Next, by administering appropriate amounts of each concentrate and a mixture of the following polymers: 66% Polimeri Europa Riblene® FF30, 19% Exxon Enable® 2005HH, and 15% Polimeri Europa Greenflex® FC45, the concentrates were blow-molded into the final formulations indicated in Tables 3 and 4 at a maximum temperature of 210°C in an industrial-scale 3-layer blow extruder (Ø 20-25-30 mm, L / D 25). The resulting 3-layer films have the same composition of polymer mixtures in all layers and therefore the same composition of stable compositions. The total thickness of the film used for Test Method B1 is 150 μm (45 μm - 60 μm - 45 μm) and the total thickness of the film used for Test Method B2 is 200 μm (60 μm - 80 μm - 60 μm). (B1) Test Method

[0157] Membrane specimens of each formulation were placed on the roof of an experimental greenhouse (geographical coordinates: 44°25'40"N, 11°16'39"E) facing south and capable of being sprayed with agricultural chemicals. The specimens were mounted on frames designed to allow direct contact with metal (galvanized iron) rods, thus simulating contact with metal supports in a real greenhouse. Treatments were performed twice a year and once a month using Fumathane 510 (a broad-spectrum sulfur-based fumigant) and Pertrin S (a chlorine-based insecticide), respectively.

[0158] After exposure, membrane samples in contact with the metal were obtained at defined time intervals and subjected to tensile testing. Residual tensile strength was measured using a Zwick® Z1.0 constant-speed tensile meter (according to modified ISO 527) to assess the degradation of the mechanical properties of the membrane samples due to polymer degradation following oxidation.

[0159] The test results are listed in Table 3. Table 3: Sulfur content of membrane samples exposed outdoors and contaminated with up to 3000 ppm. Stabilizer mixture (by weight of polymer composition) The specified elongation at break on galvanized iron after exposure to sunlight is required. Example 8 (Comparative) 0.30% of compound (A-3-1) 0.30% of compound (A-4-1) 0.05% of compound (B-1) It is immeasurable because it is 10.8 GJ / m³. 2 Then it becomes brittle. Example 9 0.30% of compound (A-3-1) 0.30% of compound (A-4-1) 0.02% of compound (B-1) 0.30% of compound (C) 16 GJ / m 2 Then it becomes 100%. The optimal elongation value is achieved after further irradiation. (B2) Test Method

[0160] Membrane specimens of each formulation were placed in a small experimental greenhouse (geographical coordinates: 44°25'40"N, 11°16'39"E), facing south and equipped with burners of the type commonly used in agricultural practice to allow elemental sulfur (a widely used fungicide) to sublimate. The burners were operated daily for three hours overnight exposure.

[0161] After exposure, membrane samples were obtained at defined time intervals and tensile tests were performed. Residual tensile strength was measured using a Zwick® Z1.0 constant-speed tensile meter (according to modified ISO 527) to assess the degradation of the mechanical properties of the membrane samples due to polymer degradation following oxidation.

[0162] The results are listed in Table 4. Table 4: Sulfur content of membrane samples exposed outdoors and contaminated with up to 15,000 ppm. Stabilizer mixture (by weight of polymer composition) Sunlight exposure to achieve 30% initial elongation at break Example 10 (Comparative) 1.20% of compound (A-4-1) 0.15% of compound (B-1) 9.2 GJ / m 2 Example 11 1.20% of compound (A-4-1) 0.05% of compound (B-1) 0.30% of compound (C) 9.4 GJ / m 2 A higher level of sunlight exposure is appropriate.

Claims

1. A stabilizer mixture comprising components (a), (b), and (c), wherein component (a) is at least one compound selected from formula (A-0), (A-1), or (A-2) or having repeating units of formula (A-3) or (A-4), wherein one or two groups A2 are hydrogen and the remaining groups A2 are propoxy, wherein a is a value from 1 to 20; wherein a is a value from 1 to 20; component (b) is at least one compound selected from formula (BI) and (B-II), wherein E2, E3, E4, and E5 are independently hydrogen, C1-C18 alkyl, phenyl, or phenyl substituted with one, two, or three C1-C4 alkyl groups; n is 1 or 2. When n is 1, E1 is a C1-C18 alkyl or an intercalated oxygen-containing C2-C18 hydroxyalkyl, and when n is 2, E1 is a bridging group of the formula -CH2CH2-OC(O)-(CH2)10-C(O)-O-CH2CH2-, wherein Q1, Q2, Q3 and Q4 are independently hydrogen, C1-C18 alkyl, hydroxylated C1-C18 alkyl, C2-C18 alkyl or intercalated oxygen-containing C2-C18 hydroxyalkyl, and T1, T2 and T3 are independently hydrogen or C1-C18 alkyl, component (c) is a compound of formula (C), and the weight ratio of component (b) to (c) is 1:50 to 50:

1.

2. The stabilizer mixture of claim 1, wherein E2, E3, E4 and E5 are independently hydrogen, C1-C4 alkyl or phenyl, Q1, Q2, Q3 and Q4 are independently hydrogen or C1-C10 alkyl, and T1, T2 and T3 are independently hydrogen or C1-C4 alkyl.

3. The stabilizer mixture of claim 1 or 2, wherein component (b) is at least one compound selected from formula (B-1), (B-2) and (B-3).

4. The stabilizer mixture of claim 1 or 2, further comprising component (d), which is at least one compound selected from formula (D-1) or having a repeating unit of formula (D-2), wherein b is a value from 2 to 20.

5. A composition comprising (I) an organic material undergoing degradation induced by light, heat, oxidation or an agrochemical compound, and (II) a mixture of stabilizers as defined in claim 1.

6. The composition of claim 5, wherein the organic material is a polyolefin.

7. The composition of claim 5 or 6 further comprises another additive selected from the group consisting of: antioxidants, slip agents, anti-sticking agents, thermoplastic fillers, pigments, anti-fogging agents and anti-hazing agents.

8. A membrane article made of the composition of claim 5.

9. The membrane product as claimed in item 8 is a single-layer membrane or a multilayer membrane having three to seven layers.

10. The membrane article of claim 8 is a multilayer membrane, wherein at least one layer contains a compound of formula (A) as defined in claim 1 and another layer contains a compound of formula (BI) or (B-II) as defined in claim 1.

11. The membrane product as claimed in item 8 is a greenhouse film covering.

12. The membrane product of claim 11, wherein the greenhouse film covering is in contact with agricultural chemical compounds.

13. A method for stabilizing an organic material against degradation induced by light, heat, oxidation or agricultural chemical compounds, comprising incorporating a mixture of stabilizers as defined in claim 1 into the organic material.