Light stabilizer mixture

Abstract

A stabilizer mixture comprising a hindered amine light stabilizer, a triazine UV absorber, and a benzophenone UV absorber.

Description

[0001] This invention relates to a stabilizer mixture comprising a hindered amine light stabilizer, a triazine UV absorber, and a benzophenone UV absorber; a composition comprising an organic material, preferably an organic polymer, that has been degraded by light, heat, oxidation, or agricultural chemical compounds; an article made from said 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:

[0003] Component (a) is at least one compound of formula (A).

[0004]

[0005] Where A1 is C2-C 18 Alkylene, C5-C7 cycloalkylene, or C1-C4 alkylene di(C5-C7 cycloalkylene),

[0006] Group A2 is independently hydrogen, C1-C 12 Alkyl, C1-C 12 Alkoxy, C5-C 12 cycloalkyl or C5-C 12 Cycloalkoxy

[0007] A3 and A4 are independently hydrogen and C1-C 12 Alkyl, C5-C 12 Cycloalkyl or groups of formula (a-1),

[0008]

[0009] Alternatively, groups A3 and A4 together with the nitrogen atoms they are bonded to form 5-10 membered heterocycles, and

[0010] a is a number from 1 to 20, and the repeating units are the same or different;

[0011] Component (b) is at least one compound selected from formulas (BI) and (B-II):

[0012]

[0013] in

[0014] E2, E3, E4, and E5 are independently hydrogen, C1-C 18 Alkyl, phenyl, or phenyl substituted with 1, 2, or 3 C1-C4 alkyl groups;

[0015] n is 1 or 2,

[0016] When n is 1, E1 is C1-C 18 Alkyl groups or C2-C groups separated by oxygen 18 hydroxyalkyl, and

[0017] When n is 2, E1 is the bridging group of the following formula: -CH2CH2-OC(O)-(CH2) 10 -C(O)-O-CH2CH2-,

[0018]

[0019] Q1, Q2, Q3, and Q4 are independently hydrogen, C1-C 18 Alkyl groups, C groups substituted with hydroxyl groups 1- C 18 Alkyl groups or C2-C groups separated by oxygen 18 Alkyl or C2-C 18 Hydroxyalkyl, and T1, T2 and T3 are independently hydrogen or C1-C. 18 Alkyl; and

[0020] Component (c) is a compound of formula (C):

[0021]

[0022] Furthermore, the weight ratio of component (b) to (c) is 1:50-50:1.

[0023] Examples of alkyl groups having up to 18 carbon atoms include 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-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.

[0024] C2-C separated by oxygen 18 Examples of hydroxyalkyl groups are those with the following formula: -CH2-CH(OH)-CH2-O-CH2-CH(C2H5)-(CH2)3-CH3.

[0025] C1-C 12 Examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, and decoxy. C1-C8 alkoxy groups are preferred, especially propoxy groups.

[0026] C5-C 12 Examples of cycloalkyl groups are cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and cyclododecyl.

[0027] C5-C 12 Examples of cycloalkoxy groups are cyclopentoxy, cyclohexyloxy, cycloheptoxy, cyclooctoxy, cyclodecoxy, and cyclododecoxy. Cyclohexyloxy is preferred.

[0028] A preferred example of a phenyl group substituted with one, two, or three C1-C4 alkyl groups is 2,4-dimethylphenyl.

[0029] C2-C 18 Examples of alkylene compounds are ethylene, propyleneene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, and hexamethylene.

[0030] An example of a C5-C7 cyclohexene alkyl group is the cyclohexene alkyl group.

[0031] An example of a C1-C4 alkylene di(C5-C7 cycloalkylene) is methylene dicyclohexylene.

[0032] When groups A3 and A4 together with the nitrogen atom to which they are bonded form a 5-10 membered heterocycle, the ring is, for example, 1-pyrrolidinyl, piperidinyl, 1-piperazinyl, 4-methyl-1-piperazinyl, or 1-hexahydroaza It is 5,5,7-trimethyl-1-homoperazinyl or 4,5,5,7-tetramethyl-1-homoperazinyl.

[0033] In the compound of formula (A), the terminal group connected to the diamino group is, for example, hydrogen or... The group; the end group connected to the triazine group is, for example, of the formula... group or formula . group.

[0034] The following stabilizer mixture contains:

[0035] A1 is C2-C 18 Alkylene, C5-C7 cycloalkylene, or C1-C4 alkylene di(C5-C7 cycloalkylene), where group A2 is independently hydrogen, C1-C 12 Alkyl, C1-C 12 Alkoxy, C5-C 12 cycloalkyl or C5-C 12 Cycloalkoxy

[0036] A3 and A4 are independently hydrogen and C1-C 12 Alkyl, C5-C 12 Cycloalkyl or a group of formula (a-1), where a is a number from 1 to 20, and the repeating units are the same or different.

[0037] The following stabilizer mixture is preferred, wherein:

[0038] A1 is a C2-C8 alkylene or cyclohexylene group, and the groups A2 are independently hydrogen, C1-C8 alkyl, or C1-C... 12 Alkoxy, cyclohexyl, or cyclohexyloxy, A3 and A4 are independently hydrogen, C1-C8 alkyl, or groups of formula (a-1), and

[0039] a is a number between 1 and 10.

[0040] E1 is a C1-C8 alkyl group.

[0041] The following formula (BI) compounds are preferred, wherein

[0042] E2, E3, E4, and E5 are independently hydrogen, C1-C4 alkyl, or phenyl. More preferably, n is 1 and E1 is C1-C4. 10 alkyl.

[0043] The following compounds of formula (B-II) are preferred, wherein

[0044] Q1, Q2, Q3, and Q4 are independently hydrogen or C1-C. 10 Alkyl, and

[0045] T1, T2, and T3 are independently hydrogen or C1-C4 alkyl groups.

[0046] Regarding component (b), the preferred compound is (BI).

[0047] The following compounds of formula (A) are preferred:

[0048]

[0049] One or two of the A2 groups are hydrogen, and the remaining A2 groups are propoxy groups.

[0050]

[0051] Where a is a number between 1 and 20, such as 1-10, 2-20, or 2-10;

[0052]

[0053] Where a is a number from 1 to 20, such as 1-10, 2-20, or 2-10.

[0054] For formulas (BI) and (B-II), the following compounds are preferred:

[0055]

[0056]

[0057]

[0058] Those formulas (B-1), (B-2), and (B-3) are highly preferred.

[0059] Most of the compounds of formulas (A) and (B) are known and can be prepared in a manner similar to that known to those skilled in the art.

[0060] Compound (A) can 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.

[0061] Compound (B) can be prepared, for example, by a method similar to that described in US-B-6,255,483.

[0062] Compound of formula (C) can be used as Purchased from BASF SE.

[0063] The weight ratio of components (a) to (b) is 50:1-24:1, preferably 45:1-24:1, more preferably 40:1-24:1, and most preferably 37:1-24:1.

[0064] The weight ratio of components (b) to (c) is preferably 1:25-25:1, more preferably 1:25-5:1, and especially 1:25-1:1. A ratio of 1:20-1:2 is highly preferred, and especially 1:15-1:2.

[0065] The weight ratio of component (a) to the total weight of components (b) and (c) is preferably 1:10-50:1, more preferably 1:5-50:1, and especially 1:2-40:1. A ratio of 1:2-40:1 is highly preferred, and especially 1:1-40:1.

[0066] 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.

[0067] The weight ratio of components (a) to (c) is preferably 1:10-40:1, more preferably 1:5-30:1, and especially 1:2-20:1. A ratio of 1:1-20:1, and especially 2:1-20:1, is highly preferred.

[0068] According to another preferred embodiment, the stabilizer mixture further comprises component (d), which is at least one compound selected from formulas (D-1) and (D-2):

[0069]

[0070] Where b is a number between 2 and 20.

[0071] The weight ratio of component (a) to (d) is preferably 20:1 to 1:1.

[0072] The weight ratio of the total weight of components (a) and (d) to the weight of component (b) is 50:1-24:1, preferably 45:1-24:1, more preferably 40:1-24:1, and most preferably 37:1-24:1.

[0073] In compounds of formula (D-2), the end group attached to oxygen is, for example, hydrogen, and the end group attached to the -CO- group is, for example, -O-C1-C3 alkyl (depending on the preparation).

[0074] Another embodiment of the present invention is a composition comprising:

[0075] (I) Organic materials subjected to degradation by light, heat, oxidation, or agrochemicals, preferably organic polymers, especially polyolefins, and

[0076] (II) Stabilizer mixtures as defined above.

[0077] Examples of organic materials to be stabilized are

[0078] 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, and polyethylene (optionally crosslinked), 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).

[0079] Polyolefins, namely the monoolefin polymers (preferably polyethylene and polypropylene) exemplified in the preceding paragraph, can be obtained by various methods, particularly by the following methods:

[0080] a) Free radical polymerization (typically under high pressure and elevated temperature).

[0081] b) Catalytic polymerization using a catalyst, which typically comprises one or more metals from Group IVb, Vb, VIb, or VIII of the periodic table. These metals typically have one or more ligands, typically oxides, halides, alkoxides, esters, ethers, amines, alkyl, alkenyl, and / or aryl groups, which may be π- or σ-conjugated. These metal complexes may be in free form or immobilized on a matrix, typically on activated magnesium chloride, titanium(III) chloride, alumina, or silica. These catalysts may be soluble or insoluble in the polymerization medium. The catalyst itself may be used alone in the polymerization reaction or may be used with other activators, typically alkyl metals, metal hydrides, alkyl metal halides, alkyl metal oxides, or alkyl metals. The catalyst is a metalalkyloxane, wherein the metal is an element of Group Ia, IIa, and / or IIIa of the periodic table. The activator can be readily modified with other ester, ether, amine, or silyl ether groups. These catalyst systems are commonly referred to as Philips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene, or single-center catalysts (SSC).

[0082] Mixtures of polymers mentioned in 2.1), 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).

[0083] 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, e.g., COC), ethylene / 1-olefin copolymers (wherein the 1-olefin is generated in situ); propylene / butadiene copolymers, isobutene / isoprene copolymers, ethylene / vinylcyclohexene copolymers, ethylene / acrylic acid copolymers. Alkyl ester 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 (e.g., hexadiene, dicyclopentadiene or ethylidene norbornene); and mixtures of these 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 of these copolymers with other polymers (e.g., polyamides).

[0084] 4. Hydrocarbon resins (e.g., C5-C9), including their hydrogenated modified products (e.g., tackifiers) and mixtures of polyalkylene compounds and starch.

[0085] Homopolymers and copolymers of 1.)-4.) may have any stereostructure, including syndiotactic, isotactic, semi-isotactic or atactic; atactic polymers are preferred. Stereoblock polymers are also included.

[0086] 5. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene).

[0087] 6. Aromatic homopolymers and copolymers derived from vinyl aromatic monomers, said monomers including all isomers of styrene, α-methylstyrene, vinyltoluene, particularly all isomers of p-vinyltoluene, ethylstyrene, propylstyrene, vinylbiphenyl, vinylnaphthalene, and vinylanthracene, and mixtures thereof. The homopolymers and copolymers may have any stereostructure, including syndiotactic, isotactic, semi-isotactic, or atactic; atactic polymers are preferred. Stereoblock polymers are also included.

[0088] 6a. Copolymers comprising the above-mentioned vinyl aromatic monomers and copolymers selected from the following comonomers: ethylene, propylene, diene, nitrile, acid, maleic anhydride, maleimide, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, such as styrene / butadiene, styrene / acrylonitrile, styrene / ethylene (copolymer), styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; high-impact mixtures of styrene copolymers with other polymers (e.g., polyacrylates, diene polymers or ethylene / propylene / diene terpolymers); and block copolymers of styrene such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butene / styrene or styrene / ethylene / propylene / styrene.

[0089] 6b. Hydrogenated aromatic polymers derived from the hydrogenation of the polymers mentioned in 6.) above, especially including polycyclohexylethylene (PCHE) obtained by hydrogenation of random polystyrene, commonly referred to as polyvinylcyclohexane (PVCH).

[0090] 6c. Hydrogenated aromatic polymers derived from the hydrogenation of the polymers mentioned in 6a.) above.

[0091] Homopolymers and copolymers can have any stereostructure, including syndiotactic, isotactic, semi-isotactic, or atactic; atactic polymers are preferred. Stereoblock polymers are also included.

[0092] 7. Graft copolymers of vinyl aromatic monomers (such as styrene or α-methylstyrene), such as styrene-grafted polybutadiene, styrene-grafted polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) grafted polybutadiene; styrene, acrylonitrile and methyl methacrylate grafted polybutadiene; styrene and maleic anhydride grafted polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide grafted polybutadiene; styrene and maleimide grafted polybutadiene; styrene and alkyl acrylate or alkyl methacrylate grafted polybutadiene; styrene and acrylonitrile grafted ethylene / propylene / diene terpolymer; styrene and acrylonitrile grafted polyalkyl acrylate or polyalkyl methacrylate; styrene and acrylonitrile grafted acrylate / butadiene copolymers, and mixtures thereof with copolymers listed in 6), such as mixtures of copolymers of polymers called ABS, MBS, ASA or AES.

[0093] 8. Halogenated polymers, such as polychloroprene, chlorinated rubber, chlorinated or brominated copolymers of isobutylene and isoprene (halobutadiene rubber), chlorinated or chlorosulfonated polyethylene, copolymers of ethylene and vinyl chloride, epichlorohydrin homopolymers and copolymers, especially polymers of 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.

[0094] 9. Polymers derived from α,β-unsaturated acids and their derivatives, such as polyacrylates and polymethacrylates; polymethyl methacrylate, polyacrylamide and polyacrylonitrile, which are modified with butyl acrylate for impact resistance.

[0095] The copolymers of monomers mentioned in 10.9.) or copolymers of monomers with other unsaturated monomers, such as acrylonitrile / butadiene copolymer, acrylonitrile / alkyl acrylate copolymer, acrylonitrile / alkoxyalkyl acrylate, acrylonitrile / vinyl halide copolymer, or acrylonitrile / alkyl methacrylate / butadiene terpolymer.

[0096] 11. Polymers derived from unsaturated alcohols and amines or their acyl 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 1.) above.

[0097] 12. Homopolymers and copolymers of cyclic ethers, such as polyalkylene glycols, polyethylene oxide, polypropylene oxide, or copolymers thereof with diglycidyl ethers.

[0098] 13. Polyacetals such as polyoxymethylene and those containing ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethane, acrylate or MBS.

[0099] 14. Polyphenylene ether and polyphenylene sulfide, and mixtures of polyphenylene ether with styrene polymers or polyamides.

[0100] 15. Polyurethane, which is derived on the one hand from hydroxyl-terminated polyethers, polyesters or polybutadiene, and on the other hand from aliphatic or aromatic polyisocyanates and their precursors.

[0101] 16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or derived from aminocarboxylic acids or corresponding lactams, 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 obtained from m-xylenediamine and adipic acid; polyamides prepared from hexamethylenediamine with isophthalic acid and / or terephthalic acid in the presence or absence of an elastomer as a modifier. Amines, such as poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and block copolymers of the above polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, such as block copolymers with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; and polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide system).

[0102] 17. Polyurea, polyimide, polyamide-imide, polyetherimide, polyesterimide, polyvinylurea, and polybenzimidazole.

[0103] 18. Polyesters derived from dicarboxylic acids and diols and / or derived from hydroxycarboxylic acids or corresponding lactones or lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate, polyalkylene naphthalate and polyhydroxybenzoate, and coether esters derived from hydroxyl-terminated polyethers; and polyesters modified with polycarbonate or MBS. Copolyesters may include, for example (but not limited to): polybutylene succinate / butylene terephthalate, polybutylene adipate / butylene terephthalate, polytetramethylene adipate / tetramethylene terephthalate, polybutylene succinate / butylene adipate, polybutylene succinate / carbonate, poly-3-hydroxybutyrate / 3-hydroxyoctanoate copolymer, poly-3-hydroxybutyrate / 3-hydroxyhexanoate / 3-hydroxydecanoate terpolymer. In addition, aliphatic polyesters may include, for example (but not limited to): poly(hydroxyalkanoates), particularly polypropylene lactone, polybutyrolactone, polyneoprolactone, polypentolactone and polycaprolactone, polyethylene succinate, polypropylene succinate, polybutylene succinate, polyhexamethylene succinate, polyethylene adipate, polypropylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene oxalate, polypropylene oxalate, polybutylene oxalate, polyhexamethylene oxalate, polyethylene sebacate, polypropylene sebacate, polybutylene sebacate and polylactic acid (PLA) and corresponding polyesters modified with polycarbonate or MBS. The term "polylactic acid (PLA)" refers to a homopolymer preferably poly-L-lactide and any blend or alloy thereof with other polymers; a copolymer of lactic acid or lactide with other monomers, such as hydroxycarboxylic acids like glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvalerate, 5-hydroxyvalerate, 6-hydroxyhexanoic acid and their cyclic forms; the term "lactic acid" or "lactide" includes L-lactic acid, D-lactic acid, mixtures thereof and dimers, namely L-lactide, D-lactide, mesolactide and any mixture thereof.

[0104] 19. Polycarbonate and polyester carbonate.

[0105] 20. Polyketone.

[0106] 21. Polysulfone, polyethersulfone and polyetherketone.

[0107] 22. Crosslinked polymers, which are derived from aldehydes on the one hand and from phenols, ureas and melamines on the other, such as phenol / formaldehyde resin, urea / formaldehyde resin and melamine / formaldehyde resin.

[0108] 23. Dry and non-dry alkyd resins.

[0109] 24. Unsaturated polyester resins, derived from copolyesters of saturated and unsaturated dicarboxylic acids and polyols and vinyl compounds as crosslinking agents, and their low-flammability halogenated modified products.

[0110] 25. Crosslinkable acrylic resins derived from substituted acrylates, such as epoxy acrylates, urethane acrylates, or polyester acrylates.

[0111] 26. Alkyd resins, polyester resins, and acrylate resins crosslinked with melamine resin, urea resin, isocyanate, isocyanurate, polyisocyanate, or epoxy resin.

[0112] 27. Crosslinked epoxy resins derived from aliphatic, alicyclic, heterocyclic or aromatic glycidyl compounds, such as the diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with conventional curing agents such as acid anhydrides or amines, with or without an accelerator.

[0113] 28. Natural polymers such as cellulose, rubber, gelatin and their chemically modified homologues, such as cellulose acetate, cellulose propionate and cellulose butyrate, or cellulose ethers, such as methylcellulose; and rosin and its derivatives.

[0114] 29. Blends of the above polymers (polymer blends), 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 / PA 6,6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC.

[0115] 30. Natural and synthetic organic materials, which are pure monomeric compounds or mixtures of such compounds, such as mineral oils, 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, typically those used as spinning compositions, and aqueous emulsions of these materials.

[0116] 31. Aqueous emulsions of natural or synthetic rubber, such as natural latex or latex of carboxylated styrene / butadiene copolymer.

[0117] The organic material is preferably a polyolefin, more preferably a polyolefin selected from linear low-density polyethylene, low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-butyl acrylate copolymer and polypropylene homopolymer or copolymer.

[0118] The stabilizer mixture of the present invention may be present in the organic material to be stabilized in an amount preferably 0.005-10% or 0.005-5%, particularly 0.01-2.5% or 0.05-2%, relative to the weight of the organic material.

[0119] The components of the stabilizer mixture of the present invention can be added individually or in combination to the organic material to be stabilized. They can be added to the polymer before, during, or after polymerization, or before or after crosslinking.

[0120] The stabilizer composition of the present invention, or its components thereof, can be incorporated into the organic material to be stabilized by known methods, such as before or during molding, or by applying a dissolved or dispersed stabilizer to the organic material, followed by solvent evaporation if necessary. The stabilizer can be added to the organic material in the form of powder, granules, or masterbatch, wherein the stabilizer is contained at a concentration of, for example, 2.5-90% by weight, preferably 2.5-25% by weight.

[0121] Examples of processing or transformation of materials stable according to the present invention are as follows:

[0122] Injection blow molding, extrusion, blow molding, rotational molding, in-mold decoration (back injection), slush molding, injection molding, co-injection molding, molding, compression molding, pressing, film extrusion (cast film; blown film), fiber spinning (textile, non-textile), stretching (uniaxial, biaxial), annealing, deep drawing, calendering, mechanical conversion, sintering, co-extrusion, coating, lamination, crosslinking (radiation, peroxide, silane), vapor deposition, welding, gluing, vulcanization, thermoforming, tube extrusion, profile extrusion, sheet extrusion, sheet casting, spin coating, bundling, foaming, recycling / reprocessing, extrusion coating, tack reduction (peroxide, thermal), fiber meltblown, spunbond, surface treatment (corona discharge, flame, plasma), sterilization (using gamma rays, electron beam), casting polymerization (R&M method, RAM extrusion), gel coating, tape extrusion, GMT method, SMC method, plastisol and impregnation (PVC, latex).

[0123] In addition, the stabilized material may also contain various conventional additives, such as:

[0124] 1. Antioxidants

[0125] 1.1 Alkylated monophenolsFor 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-(α-methylcyclohexyl)-4,6-dimethylphenol, 2,6-di(octadecyl)-4-methylphenol, 2,4, 6-Tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, and nonylphenols with linear or branched side chains, such as 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1'-methylundecane-1'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadecane-1'-yl)phenol, 2,4-dimethyl-6-(1'-methyltetrazane-1'-yl)phenol, and mixtures thereof.

[0126] 1.2. Alkylthiomethylphenol For example, 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, and 2,6-di(dodecylthio)methyl-4-nonylphenol.

[0127] 1.3. Hydroquinones and Alkylated Hydroquinones Examples include 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-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, and bis(3,5-di-tert-butyl-4-hydroxyphenyl) adipic acid ester.

[0128] 1.4. Tocopherols Examples include α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol, and mixtures thereof (vitamin E).

[0129] 1.5. Hydroxylated diphenyl thioethers Examples include 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-pentylphenol), and 4,4′-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide.

[0130] 1.6. AlkylbisphenolFor example, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 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-tert-butylphenol), 2,2'-ethylbis(4, 6-Di-tert-butylphenol), 2,2'-ethylidene bis(6-tert-butyl-4-isobutylphenol), 2,2'-methylene bis[6-(α-methylbenzyl)-4-nonylphenol], 2,2'-methylene bis[6-(α,α-dimethylbenzyl)-4-nonylphenol], 4,4'-methylene bis(2,6-di-tert-butylphenol), 4,4'-methylene bis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenol) 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-dodecyl mercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)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-hydroxy-2-methylphenyl)-4-dodecylmercaptobutane, 1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

[0131] 1.7. O-, N- and S-benzyl compounds Examples include 3,5,3',5′-tetratert-butyl-4,4′-dihydroxydibenzyl ether, octadecyl 4-hydroxy-3,5-dimethylbenzyl mercaptoacetate, tridecyl 4-hydroxy-3,5-ditert-butylbenzyl mercaptoacetate, tris(3,5-ditert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-ditert-butyl-4-hydroxybenzyl)sulfide, and isooctyl 3,5-ditert-butyl-4-hydroxybenzyl mercaptoacetate.

[0132] 1.8-Hydroxybenzyl malonateExamples include 2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate di(octadecyl) ester, 2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate di(octadecyl) ester, 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate di(dodecyl mercaptoethyl) ester, and bis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

[0133] 1.9. Aromatic hydroxybenzyl compounds Examples include 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, and 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

[0134] 1.10. Triazine compounds For example, 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4-hydroxyaniline)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyaniline)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 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-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

[0135] 1.11. Benzylphosphonates For example, calcium salts of dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, di(octadecyl) 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, di(octadecyl) 5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, and monoethyl esters of 3,5-di-tert-butyl-4-hydroxybenzylphosphonate.

[0136] 1.12. Acylaminophenols For example, 4-hydroxylauroyl aniline, 4-hydroxystearoyl aniline, and N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

[0137] 1.13. Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid with the following monohydric or polyhydric alcoholsFor example, esters of methanol, ethanol, n-octanol, isooctanol, octadecyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tri(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxalamide, 3-thiadecanool, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0138] 1.14. Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with the following monohydric or polyhydric alcohols For example, esters of methanol, ethanol, n-octanol, isooctanol, octadecyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tri(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxalamide, 3-thiadecanoyl alcohol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane, and 3,9-bis[2-{3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane.

[0139] 1.15. Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid with the following monohydric or polyhydric alcohols For example, esters of methanol, ethanol, octanol, octadecyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tri(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxalamide, 3-thiadecanoyl alcohol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0140] 1.16. Esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid with the following monohydric or polyhydric alcohols For example, esters of methanol, ethanol, octanol, octadecyl alcohol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tri(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxalamide, 3-thiadecanoyl alcohol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

[0141] 1.17. Amide of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acidFor example, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine, N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, N,N′-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxalamide ( XL-1 (provided by Uniroyal).

[0142] 1.18. Ascorbic acid (Vitamin C)

[0143] 1.19. Amine antioxidantsFor example, N,N′-diisopropyl-p-phenylenediamine, N,N′-disec-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'-disec-butyl-p-phenylenediamine, diphenylamine, N-allyl diphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine such as p,p'-ditert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol Phenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, o-tolylbiguanidine, bis[4-(1',3'-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, mixtures of mono- and di-alkylated tert-butyldiphenylamine / tert-octyldiphenylamine, Mixtures of mono- and di-alkylated nonyl diphenylamine, mixtures of mono- and di-alkylated dodecyl diphenylamine, mixtures of mono- and di-alkylated isopropyl diphenylamine / isohexyl diphenylamine, mixtures of mono- and di-alkylated tert-butyl diphenylamine, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixtures of mono- and di-alkylated tert-butylphenothiazine / tert-octylphenothiazine, mixtures of mono- and di-alkylated tert-octylphenothiazine, N-allylphenothiazine, N,N,N',N'-tetraphenyl-1,4-diaminobut-2-ene.

[0144] 2. UV absorbers and light stabilizers

[0145] 2.1.2-(2′-hydroxyphenyl)benzotriazolesFor example, 2-(2′-hydroxy-5′-methylphenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole, 2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chlorobenzotriazole, 2- (3'-sec-butyl-5'-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'-octoxyphenyl)benzotriazole, 2-(3',5'-ditert-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-chlorobenzotriazole, 2-(3'-tert-butyl-5'-[2-(2-ethyl)] [2-(2-ethylhexyloxy)carbonylethyl]-2'-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'-2'-2'-hydroxyphenyl)-5 ... 2-(3'-dodecyl-2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2'-methylenebis[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; Where 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.

[0146] 2.2.2-Hydroxybenzophenones Examples include 4-hydroxy, 4-methoxy, 4-decoxy, 4-dodecoxy, 4-benzyloxy, 4,2',4′-trihydroxy and 2′-hydroxy-4,4′-dimethoxy derivatives.

[0147] 2.3. Esters of substituted and unsubstituted benzoic acidsExamples include 4-tert-butylphenyl 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.

[0148] 2.4. Acrylates Examples include ethyl α-cyano-β,β-diphenylacrylate, isooctyl α-cyano-β,β-diphenylacrylate, methyl α-methyl cinnamate, methyl α-cyano-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-methyl-p-methoxycinnamate, N-(β-methyl-β-cyanovinyl)-2-methyldihydroindole, and neopentyl tetrakis(α-cyano-β,β-diphenylacrylate).

[0149] 2.5. Nickel compounds Nickel complexes of 2,2'-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], such as 1:1 or 1:2 complexes, with or without other ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid such as methyl or ethyl esters, nickel complexes of ketoximes such as 2-hydroxy-4-methylphenylundecyl ketoxime, and nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without other ligands.

[0150] 2.6. Steric Hindered AminesExamples include 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, bis(1,2,2,6,6-pentamethyl-4-piperidinyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonate, condensate of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine with succinic acid, and N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl) Linear or cyclic condensates of hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4-piperidinyl)hydantoin triacetate, tetra(2,2,6,6-tetramethyl-4-piperidinyl)-1,2,3,4-butanetetracarboxylate, 1,1'-(1,2-ethylidene)-bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearoyl-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidinyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1, 3,8-Triazaspiro[4.5]dec-2,4-dione, bis(1-octoxy-2,2,6,6-tetramethylpiperidinyl) sebacate, bis(1-octoxy-2,2,6,6-tetramethylpiperidinyl) succinate, linear or cyclic condensates of N,N'-bis-(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine and 4-morpholinyl-2,6-dichloro-1,3,5-triazine, condensates of 2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidinyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, 2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidinyl)-1,3,5-triazine Condensations of azines with 1,2-bis(3-aminopropylamino)ethane, 8-acetyl-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)pyrrolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidinyl)pyrrolidine-2,5-dione, mixtures of 4-hexadecyloxy- and 4-stearooxy-2,2,6,6-tetramethylpiperidine, condensations of N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine with 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, 1,2-Bis(3-aminopropylamino)ethane with 2,4,6-trichloro-1,3,5-triazine and 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Registry No. [136504-96-6]); 1,6-hexanediamine with 2,4,6-trichloro-1,3,5-triazine and N,N-dibutylamine with 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Registry No. [192268-64-7]); N-(2,2,6,6-tetramethyl-4-piperidinyl)dodecylsuccinimide, N-(1,2,2,6,6-pentamethyl-4-piperidinyl)dodecylsuccinimide, 2- Undecane-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4,5]decane, the reaction product of 7,7,9,9-tetramethyl-2-cycloundecane-1-oxa-3,8-diaza-4-oxospiro[4,5]decane with epichlorohydrin, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidinyloxycarbonyl)-2-(4-methoxyphenyl)ethylene, N,N'-bisformyl-N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexamethylenediamine, diester of 4-methoxymethylenemalonic acid with 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly[methylpropyl-3- [oxy-4-(2,2,6,6-tetramethyl-4-piperidinyl)]siloxane, maleic anhydride-α-olefin copolymers with 2,2,6,6-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-triazine, 1-(2-hydroxy-2-methylpropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, 5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, Sanduvo r(Clariant; CAS Registry No. [106917-31-1]), 5-(2-ethylhexanoyl)oxymethyl-3,3,5-trimethyl-2-morpholinone, 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidin-4-yl)butylamino]-6-chloro-s-triazine with N,N′-bis(3-aminopropyl)ethylenediamine), 1,3,5-tris(N-cyclohexyl-N-(2,2,6,6-tetramethylpiperazin-3-one-4-yl)amino)-s-triazine, 1,3,5-tris(N-cyclohexyl-N-(1,2,2,6,6-pentamethylpiperazin-3-one-4-yl)amino)-s-triazine,

[0151] 2.7. OxalideExamples include 4,4'-dioctyloxyoxalyl aniline, 2,2'-diethoxyoxalyl aniline, 2,2'-dioctyloxy-5,5'-di-tert-butyloxalyl aniline, 2,2'-di(dodecyloxy)-5,5'-di-tert-butyloxalyl aniline, 2-ethoxy-2'-ethyloxalyl aniline, N,N'-bis(3-dimethylaminopropyl)oxalamide, 2-ethoxy-5-tert-butyl-2'-ethyloxalyl aniline and mixtures thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butyloxalyl aniline, mixtures of o- and p-methoxydisubstituted oxalyl anilines, and mixtures of o- and p-ethoxydisubstituted oxalyl anilines.

[0152] 2.8.2-(2-hydroxyphenyl)-1,3,5-triazineFor example, 2,4,6-tris(2-hydroxy-4-octoxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propoxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-tetrazoloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butoxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropoxy)phenyl]-4,6-bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy / decyloxyphenyl ... [2-[2-hydroxy-2-hydroxypropoxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2- ... ]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropoxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(4-[2-ethylhexyloxy]-2-hydroxyphenyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(4-biphenyl)-6-[(2-hydroxy4-(2-ethylhexyloxy)phenyl]-1,3,5-triazine.

[0153] 3. Metal deactivatorsFor example, N,N'-diphenyloxamide, N-salicylaldehyde-N'-salicylhydrazide, N,N'-bis(salicyl)hydrazide, N,N'-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, 3-salicylamino-1,2,4-triazole, bis(benzylidene)oxalyldihydrazide, oxaloyl aniline, isophthaloyldihydrazide, sebacate bisphenylhydrazide, N,N'-diacetylhexadiazine, N,N′-bis(salicyl)oxalyldihydrazide, N,N′-bis(salicyl)thiopropionyldihydrazide.

[0154] 4. Phosphites and phosphonites Examples include triphenyl phosphite, diphenylalkyl phosphite, diphenyl phosphite, tri(nonylphenyl) phosphite, trilauryl phosphite, tri(octadecyl) phosphite, distearate pentaerythritol diphosphite, tri(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and bis(2,6-di-tert-butyl-4-methylphenyl) Pentaerythritol diphosphite, diisodecoxy pentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl) pentaerythritol diphosphite, tripearylsorbitol triphosphite, tetra(2,4-di-tert-butylphenyl) 4,4′-biphenyl diphosphonate tetra(2,4-di-tert-butylphenyl) ester, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphatacyclopenta ... Bis(2,4-di-tert-butyl-6-methylphenyl) methyl ester, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyldibenzo[d,g]-1,3,2-dioxaphosphata-octacyclo[2,2',2”-nitro[triethyltri(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite], (3,3',5,5'-tetra-tert-butyl-1,1′-biphenyl-2, 2′-Dimethyl) 2-ethylhexyl phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirane, a mixture of 2,4-bis(1,1-dimethylpropyl)phenyl and 4-(1,1-dimethylpropyl)phenyl triesters (CAS: 939402-02-5), triphenyl phosphite, and poly(oxy(methyl-1,2-ethanediyl))C with α-hydro-ω-hydroxyl groups. 10-16 Alkyl ester (CAS: 1227937-46-3).

[0155] The following phosphites are particularly preferred: tris(2,4-di-tert-butylphenyl) phosphite ( 168, CibaSpecialty Chemicals Inc.), Tris(nonylphenyl) phosphite,

[0156]

[0157]

[0158] 5. Hydroxylamine Examples include N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-di(tetradecyl)hydroxylamine, N,N-di(hexadecyl)hydroxylamine, N,N-di(octadecyl)hydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, and N,N-dialkylhydroxylamine derived from hydrogenated tallow fatty amines.

[0159] 6. Nitroketone Examples include N-benzyl-α-phenyl nitrone, N-ethyl-α-methyl nitrone, N-octyl-α-heptyl nitrone, N-lauryl-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-heptadecyl-α-heptadecyl nitrone, and nitrone derived from N,N-dialkylhydroxylamine (derived from hydrogenated tallow fatty amine).

[0160] 7. Thiosynergists For example, dilauryl thiodipropionate, dimyristyl thiodipropionate, distearate thiodipropionate, or distearate disulfide.

[0161] 8. Peroxide scavenger For example, esters of β-thiodipropionic acid, such as lauryl ester, stearyl ester, myristyl ester or tridecyl ester, zinc salts of mercaptobenzimidazole or 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, di(octadecyl)disulfide, pentaerythritol tetra(β-dodecylmercapto)propionate.

[0162] 9. Polyamide stabilizers For example, copper salts and divalent manganese salts combined with iodine and / or phosphorus compounds.

[0163] 10. Alkaline co-stabilizer Examples include melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, and alkali metal and alkaline earth metal salts of higher fatty acids, such as calcium stearate, zinc stearate, and so on. Magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocate or zinc pyrocate.

[0164] 11. Nucleating agent Examples of suitable materials include inorganic substances such as talc, metal oxides such as titanium dioxide or magnesium oxide, preferably phosphates, carbonates, or sulfates of alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and their salts, such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate, or sodium benzoate; and polymeric compounds such as ionic copolymers (ionomers). Particularly preferred are 1,3:2,4-bis(3′,4'-dimethylbenzyl)sorbitol, 1,3:2,4-bis(p-methylbenzyl)sorbitol, and 1,3:2,4-bis(benzyl)sorbitol.

[0165] 12. Fillers and reinforcing agents Examples include calcium carbonate, silicates, surface-treated silica (as described 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 other powders or fibers of natural products, and synthetic fibers.

[0166] 13. Other additives Examples include plasticizers, lubricants, emulsifiers, pigments, rheology modifiers, catalysts, flow regulators, fluorescent whitening agents, flame retardants, antistatic agents, and foaming agents.

[0167] 14. Benzofuranones and indomanones For example, those disclosed in US4,325,863, US4,338,244, US5,175,312, US5,216,052, US5,252,643, DE-A-4316611, DE-A-4316622, DE-A-4316876, EP-A-0589839, EP-A-0591102, EP-A-1291384, or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3'-bis[5, 7-Di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one, 5,7-Di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,5-dimethyl-4-neopentyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2-acetyl-5-isooctylphenyl)-5-isooctylbenzofuran-2-one.

[0168] The weight ratio of the stabilizer mixture of the present invention to the total amount of conventional additives can be, for example, 100:1-1:1000, 10:1-1:100, 20:1-1:20, or 10:1-1:10.

[0169] Another embodiment of the invention is a composition that additionally includes other additives selected from antioxidants, slip agents, anti-caking agents, thermal fillers, pigments, anti-fog agents, and anti-mist agents.

[0170] The stable material according to the invention can be used in various forms, such as as a membrane, fiber, tape, molding composition, profile, or as a base for paint, adhesive, or putty.

[0171] More specifically, the stable material according to the present invention can be used to prepare the following devices:

[0172] I-1) Automotive applications, particularly bumpers, dashboards, batteries, rear and front panels, molded parts under the hood, hood racks, cabin linings, interior linings, airbag covers, electronic molded parts for accessories (lighting), dashboard panes, headlight glass, instrument panels, exterior linings, interior trim, automotive lighting, headlights, side lights, taillights, parking lights, interior and exterior trim; door panels; fuel tanks; front side windows; rear windows; seat backs, exterior panels, wire insulation, extruded profiles for sealing, cover layers, strut hoods, chassis parts, exhaust systems, fuel filters / fillers, fuel pumps, fuel tanks, body molded parts, folding roofs, exterior mirrors, exterior trim, fasteners / fixtures, front-end molds, glass, hinges, vehicle locking systems, luggage / roof racks, pressed / stamped parts, seals, side impact beams, sound insulation / heat insulation, and sunroofs.

[0173] I-2) Equipment for aircraft, railways, and motor vehicles (cars, motorcycles), including furnishings.

[0174] I-3) Space application devices, particularly rockets and satellites, such as reentry shields.

[0175] I-4) Building and design installations, mining tools, noise reduction systems, street safety islands and shelters.

[0176] II-1) Appliances, especially washing machines, drum ovens, ovens (microwave ovens), dishwashers, mixers and irons.

[0177] II-2) Foil for use in condensers, refrigerators, heating devices, air conditioners, electronic packaging, semiconductors, coffee machines and vacuum cleaners.

[0178] III-1) Industrial products, such as gears, sliding fittings, washers, screws, bolts, handles and buttons.

[0179] III-2) Rotor blades, fan and wind turbine blades, solar panels, swimming pools, swimming pool covers, pool linings, water tank linings, closets, wardrobes, partitions, slatted walls, folding walls, roofs, louvers (e.g., roller blinds), fittings, connections between pipes, sleeves, and conveyor belts.

[0180] III-3) Profiles of any geometry (pane) and siding.

[0181] III-4) Glass substitutes, especially extruded sheets, for use in buildings (monolithic, double-walled or multi-walled), aircraft, schools, extruded sheets, window films for architectural glass assembly, trains, transportation, sanitary products and greenhouses.

[0182] III-5) Boards (walls, cutting boards), extruded coatings (photo paper, Tetra Pak and pipe coatings), silos, wood substitutes, plastic wood, wood composites, walls, surfaces, furniture, decorative foil, floor coverings (interior and exterior applications), flooring, grooved siding and tiles.

[0183] III-6) Cement-, concrete-, composite material applications and coverings, wall panels and cladding, handrails, railings, kitchen countertops, roofs, roofing panels, tiles and waterproofing fabrics.

[0184] IV-1) Boards (walls and cutting boards), trays, artificial turf, astroturf, artificial coverings for gymnasium circular fields (sports), artificial flooring for gymnasium circular fields (sports), and tape.

[0185] V-1) General purpose plastic films (packaging, dumping grounds, lamination, pool covers, waste bags, wallpaper, stretch and shrink packaging, raffia, desalination films, battery packs and connectors).

[0186] V-2) Agricultural films (greenhouse coverings, tunnels, mulches, silage, bale packaging), especially in cases of intensive application of agricultural chemicals.

[0187] VI-1) Food packaging and packaging materials (flexible and sturdy), BOPP, BOPET, bottles.

[0188] VI-2) Cartridges, syringes, medical devices, containers for any transport, garbage baskets and waste bins, waste bags, boxes, garbage bins, box liners, wheel boxes, general containers, cans for water / used water / chemicals / gas / oil / gasoline / diesel; can liners, boxes, crates, battery boxes, water tanks, medical devices such as pistons, ophthalmic instruments, diagnostic devices, and pharmaceutical blister packs.

[0189] VII-1) A device for filling polymers (talc, chalk, clay (kaolin), calcium silicate rock, pigment, carbon black, TiO2, mica, nanocomposite materials, dolomite, silicates, glass, asbestos).

[0190] Therefore, another embodiment of the invention is an article made from the composition described above. Preferred are agricultural plastic articles, preferably films, which are typically obtained using blow molding extrusion technology. Of particular interest are single-layer films or multilayer films of three, five, or seven layers, preferably with a thickness of 180 micrometers or 120 micrometers, typically 60-100 micrometers. The most important application of plastic films in agriculture is as coverings for greenhouses and tunnels, thereby enabling the cultivation of crops in a protected environment.

[0191] It is also preferred to use a multilayer film, preferably a multilayer polyolefin film, especially 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.

[0192] This multilayer membrane is typically made of three, five, or seven layers. This can result in membrane structures such as ABA, ABC, ABCBA, ABCBD, ABCDCBA, or AABCBAA. A, B, C, and D represent the different polymers and thickeners mentioned below.

[0193] However, adjacent layers can also be connected, so that the final membrane product can be made of an even number of layers, i.e., two, four or six layers, such as AABA, AABB, AABAA, ABBAA, AABCB, AABCAA, etc.

[0194] Films containing one of the aforementioned light stabilizers are typically made of low-density polyethylene (from free radical polymerization or linear type), 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 high-density polyethylene. This can include multiple layers of the same polymer type or initial polymer and re-milled or recycled polymer with different viscosities or comonomer contents (e.g., vinyl acetate content). This can include strength layers of polyamide 6 and polyamide 6.6 or adhesive layers of polyisobutylene, maleic anhydride-grafted polyethylene, maleic anhydride-grafted polypropylene, or biodegradable resin layers. The combination is optimized, for example, to maximize the initial mechanical properties of the plastic article (tensile strength, puncture resistance, impact resistance, elongation), improve interlayer adhesion strength, or achieve its specific functions (gas barrier, transparency, heat sealability).

[0195] The stabilizer mixture of the present invention is particularly suitable for stabilizing greenhouse film coverings that are in contact with agricultural chemical compounds such as metam-sodium (N-methyl dithiocarbamate), cymoxanil (2-cyano-N-[(ethylamino)carbonyl]-2-(methoxyimino)acetamide), thiram (bis(dimethylthiocarbamoyl) disulfide), mancozeb (ethylene bis(dithiocarbamate Mn-Zn)) or elemental sulfur, especially elemental sulfur or metam-sodium.

[0196] Therefore, another embodiment of the present invention is a greenhouse film covering that comes into contact with agricultural chemical compounds.

[0197] Another embodiment of the present invention is a method for stabilizing an organic material, preferably an organic polymer, to prevent degradation caused by light, heat, oxidation or agricultural chemical compounds, the method comprising incorporating a mixture of stabilizers as defined above into the organic material.

[0198] The invention is illustrated in more detail in the following examples. Unless otherwise stated, all percentages and parts are by weight. Example:

[0199] The stabilizers listed in Table 1-4 below:

[0200] Compound (A-3-1):

[0201]

[0202] Where a is a number between 1 and 10.

[0203] Compound (A-4-1):

[0204]

[0205] Where a is a number between 1 and 10.

[0206] Compound (B-1):

[0207]

[0208] Compound (B-2):

[0209]

[0210] Compound (B-3):

[0211]

[0212] Compound (C):

[0213]

[0214] Compound (D-1):

[0215]

[0216] Compound (D-2):

[0217]

[0218]

[0219] Where b is a number between 2 and 10.

[0220] Application Examples 1-7

[0221] A) Preparation of membrane samples :

[0222] Stabilization of LDPE (low-density polyethylene) multilayer films: Preparation of films containing LDPE powder (Polimeri Europa) FC 30 is characterized by a density of 0.922 g / cm³. 3 A formulation containing 0.27 g of melt flow index (190°C / 2.16 kg), 0.04 wt% of tris{2,4-di-tert-butylphenyl} phosphite relative to LDPE, 0.01 wt% of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate relative to LDPE, and a mixture of stabilizers shown in Tables 1 and 2 was prepared. The formulations were mixed in a turbine mixer. The formulations were then tested on a laboratory-scale single-screw Collin extruder. Extrusion was performed in L / D = 25 at a maximum temperature of 200°C. Then, each final formulation was tested on a laboratory scale. Layer blow molding extruder ( The film was blow-molded at a maximum temperature of 210°C in L / D 25 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).

[0223] B) Test methods

[0224] The prepared films were subjected to agrochemical treatment prior to artificial aging. Film samples of each formulation were mounted in a small experimental greenhouse (geographic coordinates: latitude 44°25'40"N, longitude 11°16'39"E), where two burners used in conventional agricultural practices were set up to allow elemental sulfur (a widely used fungicide) to sublimate. So-called "sulfur combustion" was carried out continuously for 13 days, 6 hours per day, while the films were mounted in the small experimental greenhouse. The film samples were covered with an additional single sheet of opaque film to minimize direct exposure to sunlight, thereby minimizing the effects of solar radiation and thus minimizing variability in exposure among samples in subsequent test series. The amount of sulfur burned was adjusted and aging conditions were closely monitored to obtain the desired sulfur contamination level in the film samples (measured by inductively coupled plasma).

[0225] Following agricultural chemical treatment, membrane samples of each formulation were exposed to Atlas Weather-O-Meter (WOM, according to ASTM G155, 0.35 W / m²). 2 Photoaging was accelerated by exposure to 340 nm (drying cycle). After exposure, film samples were removed at specified time intervals and subjected to tensile tests. The Z1.0 constant speed tensile tester (according to revised ISO 527) measures residual tensile strength to assess the degradation of mechanical properties of film samples due to polymer degradation after oxidation.

[0226] The test results are listed in Tables 1 and 2.

[0227] Table 1: Membrane samples contaminated with sulfur levels up to 5000 ppm and exposed to WOM.

[0228]

[0229]

[0230] High values ​​are required.

[0231] Table 2: Membrane samples contaminated with sulfur levels up to 5000 ppm and exposed to WOM.

[0232]

[0233] High values ​​are required.

[0234] Application Examples 8-11

[0235] A) Preparation of membrane samples :

[0236] Preparation of stabilized LDPE (low-density polyethylene) / LLDPE (linear low-density polyethylene) / EVA (ethylene-vinyl acetate copolymer) multilayer film samples:

[0237] Prepare a mixture of stabilizers containing a total of 20% of the LDPE powder (Polimeri Europa) shown in Tables 3 and 4 below. FC 30 is characterized by a density of 0.922 g / cm³. 3 A concentrated formulation containing 0.27 g of tris{2,4-di-tert-butylphenyl} phosphite (0.04 wt% relative to LDPE) and 0.01 wt% of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (0.01 wt% relative to LDPE) was prepared. The formulation was mixed in a turbine mixer. The formulations were then extruded using a laboratory-scale twin-screw Comac extruder. Extrusion was performed at a maximum temperature of 200°C in a solution with an L / D ratio of 32. Then, a mixture of appropriate amounts of each concentrated formulation and the following polymer was added by metering: 66% Polimeri Europa FF30, 19% Exxon 2005HH and 15% Polimeri Europa FC45, a 3-layer blow molding extruder for industrial-scale processing of concentrates ( The final formulation shown in Tables 3 and 4 was blow-molded at a maximum temperature of 210°C in L / D 25. The resulting three-layer film had the same polymer mixture composition and thus stable composition in all layers. The total film thickness was 150 μm (45 μm-60 μm-45 μm) for test method B1 and 200 μm (60 μm-80 μm-60 μm) for test method B2.

[0238] B1) Test Method

[0239] Film samples of each formulation were placed on the south-facing roof of an experimental greenhouse (geographical coordinates: latitude 44°25′40″N, longitude 11°16′39″E), where agricultural chemicals could be sprayed. The samples were mounted on a frame constructed such that the samples were in direct contact with metal (galvanized iron) rods, simulating contact with metal supports in a real greenhouse. Treatments were performed twice a year and monthly with Fumathane 510 (a sulfur-based broad-spectrum fumigant) and Pertrin S (a chlorine-based insecticide), respectively.

[0240] After exposure, the membrane samples in contact with the metal were removed at specified time intervals and subjected to tensile tests. The Z1.0 constant speed tensile tester (according to revised ISO 527) measures residual tensile strength to assess the degradation of mechanical properties of film samples due to polymer degradation after oxidation.

[0241] The test results are listed in Table 3:

[0242] Table 3: Membrane samples exposed outdoors and contaminated with sulfur levels up to 3000 ppm.

[0243]

[0244] Higher elongation values ​​after radiation are needed.

[0245] B2) Test Method

[0246] Membrane samples of each formulation were placed on the roof of a small, south-facing experimental greenhouse (geographic coordinates: latitude 44°25′40″N, longitude 11°16′39″E), where burners for conventional agricultural practices were installed to allow elemental sulfur (a widely used fungicide) to sublimate. The burners were exposed for three hours each day and operated overnight.

[0247] After exposure, membrane samples were removed at specified time intervals and subjected to tensile tests. The Z1.0 constant speed tensile tester (according to revised ISO 527) measures residual tensile strength to assess the degradation of mechanical properties of film samples due to polymer degradation after oxidation.

[0248] The test results are listed in Table 4:

[0249] Table 4: Membrane samples exposed outdoors and contaminated with sulfur levels of 15,000 ppm.

[0250]

[0251] High solar radiation levels are necessary.

Claims

1. A stabilizer mixture comprising components (a), (b) and (c), wherein: Component (a) is at least one compound selected from formulas (A-0), (A-1), (A-2), (A-3), and (A-4): (A-0) One or two of the A2 groups are hydrogen, and the remaining A2 groups are propoxy groups. (A-1) (A-2) (A-3) Where a is a number from 1 to 20; (A-4) Where a is a number from 1 to 20; Component (b) is at least one compound selected from formulas (BI) and (B-II): (B-I) in E2, E3, E4, and E5 are independently hydrogen and C1-C. 18 Alkyl, phenyl, or phenyl substituted with 1, 2, or 3 C1-C4 alkyl groups; n is 1 or 2, When n is 1, E1 is C1-C 18 Alkyl groups or C2-C groups separated by oxygen 18 hydroxyalkyl, and When n is 2, E1 is the bridging group of the following formula: -CH2CH2-OC(O)-(CH2) 10 -C(O)-O-CH2CH2-, (B-II) Q1, Q2, Q3, and Q4 are independently hydrogen, C1-C 18 Alkyl groups, C groups substituted with hydroxyl groups 1- C 18 Alkyl groups or C2-C groups separated by oxygen 18 Alkyl or C2-C 18 Hydroxyalkyl, and T1, T2 and T3 are independently hydrogen or C1-C. 18 alkyl; Component (c) is a compound of formula (C): (C) Furthermore, the weight ratio of component (b) to (c) is 1:50-50:

1.

2. The stabilizer mixture according to 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-C. 10 Alkyl, and T1, T2, and T3 are independently hydrogen or C1-C4 alkyl groups.

3. The stabilizer mixture according to claim 1, wherein component (b) is at least one compound selected from formulas (B-1), (B-2), and (B-3): (B-1) (B-2) (B-3)。 4. The stabilizer mixture according to claim 2, wherein component (b) is at least one compound selected from formulas (B-1), (B-2), and (B-3): (B-1) (B-2) (B-3)。 5. The stabilizer mixture according to any one of claims 1-4, further comprising component (d), which is at least one compound selected from formulas (D-1) and (D-2): (D-1) (D-2) Where b is a number between 2 and 20.

6. A composition comprising: (I) Organic materials that have been degraded by light, heat, oxidation, or agricultural chemical compounds, and (II) The stabilizer mixture as defined in claim 1.

7. The composition according to claim 6, wherein the organic material is a polyolefin.

8. The composition according to claim 6 or 7, further comprising other additives selected from antioxidants, slip agents, anti-caking agents, thermal fillers, pigments, anti-fogging agents, and anti-smoking agents.

9. An article made from the composition of claim 6.

10. The article according to claim 9, wherein it is a single-layer film or a multilayer film with 3-7 layers.

11. The article of claim 9, wherein it is a multilayer film comprising, in at least one layer, a compound of formula (A-0), (A-1), (A-2), (A-3) or (A-4) as defined in claim 1, and in another layer, a compound of formula (B1) or (B-II) as defined in claim 1.

12. The article of claim 11, wherein the multilayer film is a polyolefin film.

13. The article of claim 9, wherein it is a greenhouse film covering.

14. The article of claim 13, characterized in that, The greenhouse film covering comes into contact with agricultural chemical compounds.

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

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