TW200914512A - Stabilizer compositions - Google Patents

Abstract

The invention describes a mixture for the stabilization of a polypropylene-based thermoplastic polymer comprising (a) at least a compound of the formula I (b) at least a compound of the formula, and c at least a tocopherol compound, wherein component c is present in an amount of 0.0001 to 20%, based on the total weight of components (a), (b) and c.

Description

200914512 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a novel stabilizer mixture, a thermoplastic polymer based on polypropylene, and a novel stabilizer mixture, which is stabilized with polypropylene. The use of a base thermoplastic polymer for oxidation, thermal or photoinduced degradation. [Prior Art] Polypropylene-based thermoplastic polymers, such as polypropylene (PP), C 1 are susceptible to degradation due to their general construction and how these polypropylene-based thermoplastic polymers are prepared. . The third stage carbon atoms and catalyst residues allow the polypropylene based thermoplastic polymer to be easily degraded by prolonged external exposure or by auto-oxidation of the polymer at elevated temperatures (e.g., above 23 Torr). In particular, low melt flow rate (MFR) materials with melt flow rates below 2 加工 are processed at high temperatures and high shear, resulting in a stronger demand for processing virginity. In general, age/phosphite blends (IRGANOX 1010 and IRGAF〇s 168) are used in combination with acid scavengers (eg, stearic acid G (CaSt) or hydrotalcite (Hycite 713)). &. Substance scavengers centered on slaves such as certain types of lactones and fermenting stability are well known. However, to date, tocopherol has caused color or yellowing, respectively. It is surprisingly found that Irganox i 〇! RTM, Irgaf〇si 68 (rtm) and specific blends of tocopherols have been extruded in a low concentration of polypropylene-based thermoplastic polymers. Maintaining melt flow rate (mfr) and yellowing index (YI) afterwards results in excellent process stability. 200914512 [Inventive Inner Valley] According to the above description, the present invention relates to a mixture for stabilizing a polypropylene-based thermoplastic polymer comprising a) at least one compound of the formula I

(I) b) at least one compound of the formula

3

(II), and c) at least one tocopherol is based on the total weight of the components (C) present in an amount of from 1 to 2% by weight of parts (a), (b) and (c) . The component (C) preferably has a number of 15°/. , typically 0.1 to 15% basis. In a preferred mixture, for example 2 to 10%, typically 5 is from 0.001 to 15%, for example 〇.〇1 to 'in total weight of ingredients (a), (b) and (c) (c The amount is from 1 to 15%, up to 103⁄4 'based on the total weight of ingredients (a), (b) and (c) 7 200914512. In the case of a quantity of 5 ¥ a specific preferred mixture, the presence of the ingredient (C) is based on Wang / /〇, for example, 〇. . Preferably, the total weight of components (a), (b) and (c) is 4 ′, for example, 2: J component (c) is more than component (a) versus component (b) to 1:1. UI compound weight ratio of 2: 1 to

〆 where Ο -CHrCH2-〇-C-r

R, is -(CH2)r?H-CHrCHr-S-R, or (l(CH2)3~CH~(CH2)3-CH-(CH3)2 3 CH,

I is h-C: 3. Alkyl groups, and R3 are C1-C3Q groups. - an alkyl group of two 30 carbon atoms is a branched or unbranched group, for example, a methyl group, a benzyl group, a propyl group, an isopropyl group, a butyl group Secondary-butyl, tertiary-"Τ «^ base' 2-ethylbutyl'-n-pentyl'isopentyl, 丨-methyl 1-dimethylbutyl, n-hexyl, 1-methyl Base, n-heptyl, isoheptyl, bup 3' 3-tetramethylbutyl, 1 decylheptyl, 3_A 200914512 hexylheptyl-n-octyl'isooctyl, 2 _Ethyl, 1,1,3_'trimethylhexyl, 1,1,3,3-tetramethylpentyl, decyl, isodecyl, decyl, isodecyl, undecyl ,isodecyl,dodecyl,isododecyl, 1,1,3,3,5,5-hexamethylhexyl, tridecyl, tetradecyl, fifteen 'Cetyl, heptadecyl, octadecyl (stearyl), decyl or decyl. An interesting mixture is one in which component (c) is a compound of formula I, wherein Ri

For an elevation 2) 3 - i | T (CH2) Q H - Can 2) 3 - CH_ (CH3) 2 . This compound is a tocopherol, and its CH3 CH3 is commercially available under the trade name Irgan〇x E 201 (RTM) [Ciba

Specialty Chemicals Inc]. The compound of formula I is Irganox l〇1〇 (rTM) and the compound of formula n is Irgafos 168 (RTM). Both are commercially available from Ciba Specialty Chemicals Inc. 〇rp〇rati〇n. Mixtures of interest, in addition to ingredients (a), (1?) and ((In addition to 〇, additives are also included, typically shown below: JL antioxidants to

Id. Alkylation of, for example, 2' 6-di-t-butyl-4-nonylphenol, 2-tris-butyl-4,6-dinonylphenol, 2,6_di_third- Butyl_4·ethylphenol, 2,6-a-second-butyl_4_n_butylphenol, 2,6-di-t-butyl- 4-isobutylphenol' 2, 6- Dicyclopentyl-4-methylphenol, 2 sec-cyclohexyl)_4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2, 4, 6_three Cyclohexyl, 2,6-di-t-butyl-4-methyloxymethyl, fluorenyl (which is linear or branched in the side chain), such as 2,6_di-壬基_4_曱基盼, 2, 4-dimethyl_6_(1,_methyl-10-carbonated·Guangji), 2, Xinji 200914512 methyl_6_(1'-methyl ten Heptacarbonate-fluorenyl-based phenol, 2,4-dimethyl-Mr-methyltridecane-1'-yl)phenol and mixtures thereof. ^ For example 2,4-dioctylthiodecyl-6-tertiary-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthio Methyl-6-ethylphenol '2,6-di-dodecylthiomethyl-4-nonylphenol. P-diphenols, such as 2,6-di-second-butyl-4-methoxyphenol, 2,5-di-tert-butyl hydroquinone, 2,5_--second -pentyl hydroquinone, 2,6-diphenyl-4-enostearyloxyphenol, 2,6-mono-second-butyl hydroquinone, 2,5-di-third -butyl 4-hydroxyanisole, 3,5-di-tertiary-butylhydroxyanisole, 3,5-di-t-butyl-4-hydroxyphenylstearate, double (3 5_二_三______hydroxyphenyl) adipic acid S.

Li. Alkylated thiodiphenyl ether 'eg 2,2 '-thiobis(6-tri-butyl-4-methylphenol) ' 2,2,-thiobis (4-octyl) Phenol), 4,4,-thiobis(6-second-butyl-3-methylphenol), 4,4,-thiobis(6-tri-butyl-2-methylphenol), 4,4,-thiobis(3,6-di-second-pentylphenol), 4,4,-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide. 1_:_5 Burning and double-decorating, and burning and brewing, such as 2,2'-曱 bis (6-tert-butyl-4-nonylphenol), 2,2,-曱 双 double (6_ Third _ butyl _4_ethyl phenol), 2, 2 - methyl bis [4-indolyl-6-(α-methylcyclohexyl) sulphate], 2, 2, _ A shuang double (4_ A -6-cyclohexylphenol), 2,2'-methylene bis(6·fluorenyl-4-nonylphenol), 2, 2,·methyl bis(4,6-di-t-butyl) Phenol), 2,2,-ethylidene bis(4,6-di-t-butylphenol)' 2,2,-ethylidene bis(6·t-buty-4_isobutylphenol) , 2, 2 曱 双 [6-(α-曱 basic methyl) _4_壬基盼], 2, 2, - A double choice [6- 200914512

(α,α-dimercaptobenzyl)_4_nonylphenol], 4,4,methylene bis(2,6-di-second-butylphenol), 4,4, 曱 曱 bis ( 6-Terti-butyl-2-methylphenol),}, 1-bis(5-tris-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-double second -butyl-5-mercapto-2-hydroxybenzyl) 4-methylphenol, 1,1,3_tris(5_t-butyl-4-hydroxy-2-indenylphenyl)butane , 丨, Bu bis (5_Third-butyl-4-3⁄4 yl-2-mercaptophenyl)_3_N-dodecylalkyl decyl, ethylene glycol bis [3,3- bis ( 3'-Third-butyl-4,-hydroxyphenyl)butyrate], bis(3_tert-butyl-4-oxenyl-5-methyl-phenyl)dicyclopentadiene, Bis[2_〇,_T-butyl-2-hydroxy-5'-methylbenzyl)_6•Third-butyl_4_nonylphenyl]terephthalic acid vinegar, 1 '1 -bis(3,5-dimercapto-2-diphenyl)butane, 2,2-bis(3,5-di-tertiary-butyl-4-hydroxyphenyl)propane, 2, 2-bis-(5-tri-butyl-4-hydroxy-2-methylphenyl)_4_n-dodecylalkyl decyl, hydrazine, hydrazine, 5 ' 5-tetrazide (5-third -butyl·4_hydroxy-2-methylphenyl)pentane, p-oxime The butylated reaction product of phenol and dicyclopentadiene. Benzoin, such as 3, tetra-tert-butyl-4, octadecyl-4-hydroxy 4'-dihydroxydiphenylmethyl ether-3, 5-dimethylbenzene Base mercapto acetate, tridecylalkyl 4-hydroxy-3,5-di-t-butylbenzyl thioglycolate, tris(3,5-di-t-butyl -4-hydroxybenzyl)amine, bis(4_third-butyl hydrazide•hydroxy-2,6-dimethylbenzyl)dithio-terephthalic acid vinegar, double (3, 5_2 _Third_butyl_4_ mercaptobenzene 5-di-tertiary-butyl_4-hydroxybenzyl hydrazine methyl) sulfide, isooctyl-3-yl acetate. A propylated decyl ester, such as dioctadecyl-2-, 2-bis(3,5-di-t-butyl-2-hydroxyphenylmethyl)malonate, di-ten八11 200914512 Carboalkyl-2-(3-tert-butyl-4-ylhydroxy-5-methylbenzyl)malonate, di-dodecylaminoethyl-2,2 -Bis(3,5-di-t-butyl-4-hydroxybenzyl)malonate, bis[4_〇,丨,3,3-tetramethylbutyl)phenyl]_ 2 , 2_bis(3,5-di-tris-butyl-4-hydroxybenzyl)malonate. A compound of U-aryl aromatic benzoyl, such as work, 3,5_tris(3,5-di-tert-butyl-4-hydroxybenzyl)_2,4,6-trimethyl Benzene, 〖, ^ bis (3,5-di-t-butyl-butyl 4-hydroxybenzyl)_2,3,5,6-tetradecylbenzene, 2,4,6-tris (3,5 -Di-t-butyl-1,4-hydroxybenzyl)phenol. 1^2: triterpenoid tA, for example 2,4-bis(octylfluorenyl)·6_(3,5_di-third-butyl-4-hydroxyanilino)_ι,3,5_three tillage, 2_octyl fluorenyl _4, 6_ bis (3,5-di-t-butylhydroxyanilino) q,3,5_three tillage, y octyl decyl-4,6-bis (3,5- Di-t-butyl butyl 4-hydroxyphenoxy), 3, 5-diplonic, 2,4,6-tris(3,5-di-tri-butyl-4-hydroxyphenoxy) j, 2 3_dimorph, 1,3,5-di(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate ' 1,3' 5-tri (4 -Third-butyl·3_hydroxy-2,6-dimethylphenylhydrazinyl)isocyanurate, 2,4,6-tris(3,5-di-tertiary-butyl_4• Hydroxybenylethyl)-1 ' 3 ' 5 -triphthyl ' 1,3,5 -tris(3,5 -di-t-butyl-4-hydroxyphenylpropanyl)-hexahydro-1, 3,5-trimorphine, i,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate. U0. Stupid methyl stearate such as dimercapto-2,5-di-tert-butyl_4_ mercaptobenzylphosphonate, diethyl-3' 5-di-third-butyl _4_ mercaptomethylphosphonate, di-octadecyl 3,5-di-tertiary-butyl-4-ylbenzoylphosphonate, octadecylcarbyl -5-Third-butyl _4_ carbyl _3-methylbenzylphosphonate '3,5-di-second-butyl-4-per benzylmethylphosphonic acid monoethyl • 12 200914512 calcium salt. For example, stearin aniline 'octyl N-(3, phthalic acid ester. 4_ via laurel anilide, 4-hydroxy-di-di-butyl-4-phenylphenyl) ammonia

Base 1 , propionic acid and mono- or ethanol, n-octanol, iso-octanol, deca- 1,9-nonanediol, ethylene glycol, 丨'1 propane diethylene glycol, diethylene glycol, three Ethylene glycol, pentaerythritol, tris(hydroxyethyl)iso# cyanurate, N,N,-bis(hydroxyethyl)ethylenediamine diamine, 3-thiadeca-magnetic alcohol, 3 -thiazepine Pentadecyl alcohol, trimethyl hexanediol 'trimethylolpropane, 4-_ A Tianshe ▲ Dimethylmethyl-1- phenanthrene-2,6,7-trioxabicyclo[2.2.2]octane . 1.13. /5 -(5-Third-buty _/ι^. -3-methylphenyl) propionic acid and esters of polyhydrogen alcohols, such as methanol, 7 ^ ethanol, n-octanol , iso-octanol, octadecyl alcohol, 1,6-hexanediol, 1, 〇τ 11 9 壬 diol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethyl Esters of polyhydric alcohols such as methanol, octadecyl alcohol, 1,6-hexanyl alcohol, neopentyl glycol, thio

Alpha diol, diethylene glycol, triethylene glycol, pentaerythritol, bis(hydroxyethyl)isocyanurate, hydrazine, hydrazine, bis(hydroxyethyl) ethanediamine diamine, 3-thiaza Monohydric alcohol, thiefene pentadecyl alcohol, trimethyl methacrylate, trimethylolpropane, 4, ylmethylphosphorus-2,6,7-trioxy: bicyclo[2.2.2] octyl; 3 '9_双[2_{3_(3_Third_Butyl-4,yl-5-methylphenyl)propoxyphene 1, dimethyldimethylethyl]-2,4,8,1 〇_Tetraoxane snail [5.5] Eleventh Carbon Institute. Esters of propionic acid and mono- or polyhydric alcohols, such as with methanol, ethanol, octanol, octadecyl alcohol, hydrazine, 6-hexane two 13 200914512, 9-fluorene diisopropanol Alcohol, 1,2-propanediol, neopentyl glycol, sulfur diethylene glycol, triethylene glycol, pentaerythritol, soil h, cyanurate, N, N'_ bis(hydroxyethyl) ethylene dioxime Monohydric alcohol, alcohol hydrazine* (by ethylethylamine, 3-thia 4_ via carbazyl, thiopentadecanol, trimethyl hexane diol, trimethyl methacrylate, 1 "soil-1, Hetero-2,6 '7-trioxabicyclo[2,2.2]octane. Sazan t--butylphenyl and mono- or polyhydroquinones such as and methanol, ethanol 'octanol, ten Octacohol, Bu 6H I! Π9·decanediol, ethylene glycol...2-propanediol, neodecanediol, sulfur monoethyl alcohol, diethylene glycol, triethylene glycol, pentaerythritol, triethyl) Cyanurate, N, N, bis (a ^ 匕 乙基 ) ethyl) ethanediamine diamine, 3-thiaza: nal alcohol, 3-thiapentadecanol, trimethyl hexane diol, Trimethylolpropane, 4 u methylphosphonium 2 ' 6 ' 7_trioxabicyclo[m]octane. 5-di-fan_tri-butyl_4_ Lanthanum phenyl) guanidine of guanidine, such as N, Ν'-譬π, s-enough--Γ* « A t bis (--second-butyl _4. hydroxyphenyl propyl fluorenyl) hexamethylene Diamine, N, N, _ bis (3,5-di-tris-butyl-4-hydroxyphenylpropanyl)trimethyldiamine, N,N,-bis (3,5_di- Third-butyl-4-ylhydroxyphenylpropanyl)anthracene, N,N'_bis[2_(3_[3,5-di-tris-butyl-anionylphenyl]propanyloxy Ethyl]ethylenediamine diamine 1.17 · Ascorbic acid (vitamin.) 1.18. Amine antioxidant also, for example, hydrazine, hydrazine, _di-isopropyl-p-phenylenediamine, hydrazine, hydrazine -di-second-butyl-p-phenylenediamine, hydrazine, hydrazine, _bis, dimethyl pentyl)-p-phenylenediamine, Ν' Ν, - bis (ι_ethyl_3_甲甲Benzyldiamine, 对 'p-phenylenediamine, Ν ' Ν'-bis(1-methylheptyl)-p-phenylenediamine, hydrazine, hydrazine, _: cyclohexyl phenylenediamine ' Ν ' Ν '- Phenyl-p-phenylenediamine, anthracene, fluorene, bis(2-naphthyl)-p-benzene 14 200914512 Diamine, N-isopropyl-hydrazine'-phenyl-p-phenylenediamine, n- (1,3-dimethylbutyl)-indole'-phenyl-p-phenylenediamine, N-(l-methylheptyl)_;^,_phenyl_ P-phenylenediamine, N-cyclohexyl-fluorene'-phenyl-p-phenylenediamine, 4-(p-toluenesulfonium)diphenylamine, hydrazine, Ν'-dimethyl-hydrazine, hydrazine, -di-second-butyl-p-phenylenediamine, diphenylamine 'Ν-allyldiphenylamine, 4-isopropoxydiphenylamine, Ν_phenyl-1-naphthylamine , Ν-(4-tris-octylphenyl)_丨_naphthylamine, Ν_phenyl_2_heptylamine 'octylated, ·benzamine', for example, pair of '-di- Tri-octyldiphenylamine, 4-n-butylaminophenol, 4-butylaminophenol, 4-mercaptoaminophenol, 4-dodecylaminophenol, 4-eighteen Carboguanamine phenol, bis(4-methoxyphenyl)amine, 2,6-di-t-butyl-butyl-4-didecylaminomethylphenol, 2, 4,-diaminodiyl Phenyl decane, 4' 4'-diaminodiphenylmethane, hydrazine, ν, hydrazine, Ν-tetradecyl-4,4 _ monoaminodiphenyl fluorene, 1,2 - bis[ (2-methylphenyl)3⁄4yl]ethene, 1 '2-bis(phenylamino)propene, (0-tolyl) double vein, bis[4-(Γ,3'-didecyl) Butyl)phenyl]amine, third _octylated n-phenyl-1-naphthylamine, mono- and dialkylated third-butyl/ a mixture of tri-octyldiphenylamine, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, And a mixture of dialkylated isopropyl/isohexyldiphenylamine, a mixture of mono- and dimorphylated tert-butyldiphenylamine, 2,3-dihydro-3,3_ Dimethyl-4H-1,4-benzophenone: a mixture of phenothiaphine, mono- and dialkylated tert-butyl/tris-octyl morphine, mono- and dialkyl a mixture of a third octyl phenanthrene, N-allylphenothiphthyl, anthracene, anthracene, anthracene, N,-tetraphenyl-i, 4-diaminobutan-2-ene. 2. UV absorber first stabilizer 15 200914512 phenyl) benzotrisene, such as ketone _5'-methylphenyl) benzotriazole, 2_(3', 5'·di-third -butyl-2,-hydroxyphenyl)benzotriazole, 2-(5,-tris-butyl-2'-hydroxyphenyl)benzotriazole, 2_(2,_hydroxy-5'-- (l,1,3,3-tetramethylbutyl)phenyl) benzotriazole, 2_(3,,5,___second-butyl-2'-pyridylphenyl)-5- Chlorobenzotriene n-position, 2-(3,·:r-butyl-2-mercapto-5-methylphenyl)-5-gas benzotriene α, 2-(3'-second_d Base 5 - second-butyl 2'-transphenylene) benzotrimide, 2-(2,-trans-yl-4,-octyloxyphenyl)benzotriazole, 2_(3,, 5,_di-third-pentyl·2, hydroxyphenyl)benzotriazole, 2-(3,5,-bis(α,α-dimercaptophenyl)-2,-hydroxyphenyl Benzotriazole, 2-(3,·T-butyl-2-,-hydroxy-5,-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2- (3,-Terti-butyl-5,-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3 ,_third-butyl-2'-hydroxy-5 -(2-methoxycarbonylethyl)phenyl)_5-chlorobenzotriazole, 2_(3,-t-butyl- 2,-hydroxy- 5,-(2-methoxycarbonylethyl) Benzo) benzotriazole, 2-(3,-tri-butyl-2,-hydroxy-5,·(2-octyloxycarbonylethyl)phenyl)benzo-3-azole, 2-( 3,-T-butyl-5,-[2-(2-ethylhexyloxy)carbonylethyl]-2'-hydroxyphenyl)benzotriazole' 2-(3,-dodeca carbon Alkyl·2,_hydroxy_5,_methylphenyl)benzotriazole, 2-(3,-tris-butyl-2,-hydroxy-5,_(2-isooctyloxycarbonyl) Base) benzotriazole, 2,2,-methylene bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol]; a transesterification product of [3'-tris-butyl·5,-(2-hydroxycarbonylethyl)-2,-hydroxyphenyl]-2-indole-benzotriazole and polyethylene glycol 3 00; [R_CH2CH plant c〇〇_CH2CH, where R = 3, -tri-butyl-4'-hydroxy-5,-2H-benzotriazol-2-ylphenyl, 2-[2,-hydroxyl -3,-(α,α-dimethylphenylhydrazino)_5'_(i,1,3' 3-tetramethylbutyl)phenyl]benzene 200914512 tetramethylbutyl)-5,-( α,α and three° sitting; 2-[2,- a group -3,-(l,1,3-anthracene basic methyl)phenyl]benzotriazine. For example, 4-hydroxy, 4·decyloxy, 4·octyloxy, 4-decyloxy, 4_ Dodecyl alkoxy, 4-phenyloxy, 2,, 4, trihydroxy and 2,-hydroxy-4,4,-dimethoxy derivative.

Substituted benzoic acid side such as 4_second-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl stilbene, double (4_ Tris-butylphenylhydrazine) resorcinol, phenylhydrazine resorcinol, 2,4-di-tertiary-butylphenyl 3,5-di-tertiary-butyl-4-hydroxybenzene Formate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-third-butyl-4-hydroxybenzene Formate, 2-methyl-4,6-di-t-butylphenyl 3,5-di-t-butyl-4-hydroxybenzoate. L4·hexa-categorate, such as ethyl α-cyano-cold, cold-diphenyl acrylate, isooctyl α-cyano-stone, diphenyl acrylate, fluorenyl α·methoxy oxime Cinnamate, fluorenyl α-cyano-stone-fluorenyl _ρ_methoxy cinnamic acid 酉曰 'butyl ex-cyano-^3 - fluorenyl _ρ_ methoxy cinnamic acid vinegar曱 醯 醯 Ρ Ρ 甲 methoxy cinnamate and Ν-(cold-hydrazinyl-lu-cyanoethylene)-2-mercapto porphyrin. 2.5· Nickel compound, for example, 2,2′·thiobis[4-(1,1,3,3-tetradecylbutyl)-reviewed complex] like a 1: 1 or 1: 2 complex ( And with or without other ligands like n-butylamine, triethanolamine or N_cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, a nickel salt of a monoalkyl ester, such as methyl or Ethyl ester '4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid 17 200914512 Nickel salt 'ketone oxime nickel complex, such as 2 · thiopurine 4 methyl phenyl ten Nickel complex of monoalkyl ketoxime, 1-phenyl-4-moon-foamed < ν „ Nickel complex of Laurel-5-hydroxypyrazole (with or without other ligands). The steric hindrance I, for example, shot 2,, ^ J such as bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, double (2,2,6,6 field w 0,6 -tetramethyl_4_piperidinyl) succinate, bis(1,2,2,6,6-penta-pyrene/p & good T-based _4_° decyl) sebacate, Double (1-

Octyloxy-2' 2' 6' 6-tetramethyl) azelaic acid vinegar, bis, 2, 2, 6, 6-pentamethyl-4-piperidinyl)-n-butyl_3,5 Condensation product of _di-t-butyl- 4-hydroxybenzylidene vinegar, hydroxyethyl)_2, 2, 6, tetramethyl-4-hydroxypiperidine and succinic acid, N, N , double, 2,6,^ tetramethyl-4-piperidinyl)hexamethylenediamine and 4_third-octylamino 2,dichloro-1' 3 ' 5-trimized straight chain Or a cyclic condensate, tris(2,2,6,6-tetradecyl-4-bryridinyl) nitrilotriacetate, tetrakis(2,26 tetramethyl 4 base)-1 ' 2' 3,4-Dingyuan tetracarboxylate,! , 〖, _ (〗, 2_乙烧一基) - bis (3,3' 5' 5-tetramethylpiperidone), 4-benzylidene-2,2,6,6-tetradecyl Piperidine, 4_stearyloxy-2,2,6,6-tetradecylpiperidine, bis(1 '2'2'6,6-pentamethylpiperidinyl)-2-n-butyl 2-(2-hydroxy-3,5-di-second-butylphenylhydrazino)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1' 3,8-triterpenoid [4_5]decane-2,4-dione, bis(1-octyloxy-2, 2 '6' 6-tetradecylpiperidinyl) sebacate, double ( 1_octyloxy-2,2,6,6·tetramethylpiperidinyl) succinate, N,N,-bis(2,2,6,6-tetradecyl-4 fluorene a condensed product of hexamethylene diamine and 4 phenoline 2,6-dichloro-1,3,5-triphenyl straight or bismuth, 2-chloro-4,6-bis(4-positive- Condensation of butylamino 2,2,6 '6-tetramethylpiperidinyl-1,3,5-trimorphine and 1,2-bis(3-aminopropyl 200914512 amino)ethane Product, 2-gas-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidinyl, 3,5-trimorphine and 1,2- a condensed product of bis(3-aminopropylamino)ethene, 8-ethyl -3-dodecarbyl-7, 7, 9, 9-tetramethyl-1 '3,8-triterpenoid [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' 4-hexadecenyloxy- and 4-stearyloxy-2,2,6' 6-tetra a mixture of mercaptopidine, N,N,-bis(2,2,6,6-tetradecyl-4-piperidyl)hexamethylenediamine and 4-cyclohexylamino-2,6-di a condensation product of chloro-1,3,5-triazine, 1 '2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-three tillage and Condensation product of 4-butylamino-2,2,6,6-tetradecylperidine (CAS Registry Number [136504-96-6]); 1,6-hexanediamine and 2,4, Condensation products of 6-trichloro-1,3,5-three tillage and N'N-dibutylamine and 4-butylamino-2'2,6'6-tetramethylpiperidine (C AS registration number) [192268-64-7]); N-(2,2,6,6-tetradecyl-4-soleyl)-positive-dodecylsuccinimide, N-(l,2 ,2,6,6-pentamethyl_4_0 succinyl)-positive-twelve Alkyl succinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3 ' 8-diindole-4-oxo-spiro[4,5] Decane, 7,7,9,9-tetradecyl-2-cycloindole Carboalkyl-1-oxa-3,8-diindole-4-oxo-[4, decane and epigas alcohol The reaction product, 1,1-bis(1,2,2,6,6-pentamethyl-4-. d, 定, N'-bis-carbamyl-N,N,-bis (2,2,6,6-tetramethyl) Di-4-methylpiperidinyl hexamethylenediamine, 4 decyloxymalonic acid and diester of 1,2' 2,6 '6-pentamethyl-4-hydroxypiperidine, poly[methyl Propyl-3-oxy-4-(2,2' 6' 6-tetramethyl-4-nivine bite 19 200914512 base)] Shi Xi oxygenated 'maleic anhydride-α-olefin copolymer and 2 The reaction product of 2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine. 2 '4-Bis[N-(l-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-indole-butylamino]-6_(2·hydroxyethyl Amine q,3,5-trimorphine, 1-(2-carbyl-2-mercaptopropoxy)-4-octadecyloxy-2,2,6,6·tetradecyloxyl ,5-(2-ethylhexyl)oxymethyl_3,3,5-trimethyl_2_morphinone' Sanduvor (Clariant; CAS Reg. No. 106917-3 1-1), 5 -(2-ethylhexyl)oxymethyl_3,3,5•trimethyl-2-morpholinone, 2, f 4-bis[(1-cyclohexyloxy)_2' 2, a reaction product of 6,6-piperidin-4-yl]butylamino]-6-chloro-s-trin and N,N,-bis(3-aminopropyl)ethylenediamine), 1, 3 ' 5 -B (N-cyclohexyl-N-(2,2,6,6-tetramethyl)- phenan-3-one-4-yl)amino)-s-trimorphine, 1,3,5 -Tris(N-cyclohexyl-N-(l,2,2,6,6·pentamethylpipedino-3-inone-4-yl)amino)-s_trimorphine. H_ ethane di-Si diamine, such as 4,4 '-dioctyloxyxanthenil, 2' 2'-diethoxyoxalinol, 2,2,-dioctyloxy-5,5 ,-di-tertiary-butoxypropenaniline 2' 2'-di-dodecylalkoxy-5,5,-di-third-I butoxyphenidine, 2-ethoxy- 2,-ethylglyoxime, N,N,-bis(3-dimethylaminopropyl)ethylenediamine, 2-ethoxy-5-t-butyl-2,- a mixture of acetanilide and its combination with 2-ethoxy-2,-ethyl-5,4'-di-tris-butoxyanilide, o- and p-methoxy-disubstituted A mixture of oxalic acid and a mixture of o- and p-ethoxy-disubstituted oxalic acid. 2.8. 2-(2-Phenyl-based 1,3,di-morphine, for example 2,4,6-tris(2-cyano-4-octyloxyphenyl)-1,3,5-trimorphine, 2-(2-amino-4-octyloxybenzene 20 200914512 base)-4,6-bis(2'4-dimethylphenyl)-1,3,5-three tillage, 2-(2, 4-di-p-phenyl)-4'6-bis(2,4-dimethylphenyl)-1,3,5-trimorphine, 2,4-bis(2-hydroxy-4-propoxy Phenyl)_6_(2,4-dimethylphenyl)-indole, 3,5_three tillage, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis (4-A) Phenyl) ",3,5-dimorphine, 2-(2-amino-4-dodecyloxyphenyl)- 4,6-bis(2,4-dimethylphenyl)-1 , 3,5-trimorphine, 2-(2-hydroxy-4-tridecane alkoxy

Base)_4 '6-bis(2'4-dimethylphenyl)b 3' 5-triphthyl, 2-[2-pyridyl-4-(2.H-yl-3-butoxypropoxy Phenyl]_4' 6-bis(2,4-dimethyl)-1 , 3, 5-trin, 2-[2-hydroxy_4_(2_hydroxy_3_octyloxypropoxy) Phenyl]_4,6_bis(2,4-dimercapto)_1,3,5-trimorphine, 2_[4_(dodeca alkoxy/tridecacarbonyloxy-2-hydroxypropoxy) _2_hydroxyphenyl],6-bis,4-dimethylphenyl)-1,3, Hongsan, 2-[2·hydroxy-4-(2-hydroxy-3-dodecanyloxy) Propoxy)phenyl]-4,6-bis(2,4-dimercaptophenyl)4,3,5-trimorphine, 2-(2-hydroxy-4-hexyloxy)phenyl]4 , 6_diphenyl-indole, 3,5_three tillage, 2_(2_hydroxy-4-methoxyphenyl)_4,6-diphenyl_1,3,5·three tillage, 2,4, 6-bis[2-hydroxy-4-(3-butoxy-2.hydroxypropyloxy)phenyl],3,5-trimorphine, 2-(2-hydroxyphenyl)_4_(4_oxime Phenyl) _6• stupid 丨, 3,% trimorphine, 2-{2-hydroxy-4-[3-(2-ethylhexyl_1_oxy)_2-hydroxypropoxy]phenyl }_ 4,6-bis(2,4-dimethylphenyl)^,3,5·trisyl. 3. Metal deactivators, such as N,N,-diphenyl oxalate diamine, N-salicylaldehyde-N1-salt, N,N,-double (water 醯) 胼, N , n,-bis(3,5-di-second-butylhydroxyphenylpropanyl)indole, 3-salicylidene-1,2,4-diazole, double (clumsy) Dioxalate diacetate, oxalic acid anilide, diterpene bismuth citrate, bis-phenyl hydrazine sebacate, N,N, _diethyl decyl adipate dihydrazide 21 200914512 spell, N ' Ν' - Double - (Water Yang Brewing) B. Two brewing two ploughing, N, N, _ double _ (water simmering) thiopropionate diterpenoid. Linoleic acid vinegar - for example, triphenyl phosphite vinegar, diphenyl alkyl phosphite vinegar, phenyl dialkyl phosphite tris(nonylphenyl) phosphite, trilauryl phosphite, three _ octadecyl phosphite, distequine pentaerythritol diphosphite, tris(2,4-di-t-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, Bis(2,4-di-tris-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-cumylphenyl)pentaerythritol diphosphite, bis(2,6-di- Tris-butyl fluorenyl) pentaerythritol diphosphite, diisodecyloxy pentaerythritol diphosphite, bis(2,4-di-second-butyl-6-nonylphenyl) pentaerythritol di-square Acid ester, bis(2' 4' 6-di(tris-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetra (2,4_di_third_d Phenyl) 4,4, diphenylene diphosphinate '6_isooctyloxy·2,4,8,ι〇_tetra-tert-butyl 12Η a [d,g]-1 , 3,2-dioxaphosphocin, double (2' 4-di- Tri-butyl-6-methylphenyl)methylphosphite, bis(2,4·di-t-butyl-6-methylphenyl)ethyl phosphite, 6-fluoro-2 ,4,8, 10-tetra-tris-butyl-12-fluorenyl-diphenyl[d,g]-l,3,2-dioxaphosphine, 2' 2,2''-minorous nitrogen [Triethyltris(3,3',5,5'-tetra-tertiary-butyl-1, fluorene-diphenyl-2,2'-diyl) phosphite], 2·ethyl Hexyl (3,3,5,5'-tetra-tertiary-butyl-1,ι'_diphenyl-2,2'-diyl) phosphite, 5-butyl-5-ethyl -2-(2 ' 4' 6-tri-tert-butylphenoxy;) _!, 3,2-dioxaphosphirane 〇 5. Hydroxylamines such as N,N-dibenzyl Hydroxylamine, N,N-diethyl 22 200914512 * transamine, N,N-dioctylhydroxylamine, n,N-dilaurylhydroxylamine, N,N-di-hexadecylhydroxylamine, n,N-di-octadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N- derived from hydrogenated aliphatic amine Dialkylhydroxylamine. Jingkeesone such as N-benzyl-1-phenylnitrone, N-ethyl-α-methylnitrone, Ν-octyl-α-heptyl nitrate , Ν_lauryl _ α _ undecyl nitrone, Ν-tetradecyl-α _ tridecyl nitrone, Ν _ hexadecyl _ α _ pentadecyl nitrate Ketone, Ν-octadecyl _ α _ heptadecyl nitrone, f; N-hexadecyl _α_heptadecyl nitrone, N octadecyl fifteen carbon Alkyl nitrone, Ν-heptadecylalkyl·α • heptadecyl nitrone, hydrazine-octadecyl-hexadecylalkyl nitrone, hydrazine derived from hydrogenated aliphatic amine, Ν _ The alkyl group is derived from a base amine; 5 ketone. 7 second soul _ generation synergy 1 ′ such as dilauryl thiodipropionate, DIMISTRYL stone dangerous dipropionic acid brewing, ^ stearin thiodipropionate or distearyl disulfide.

Li oxidized face, such as esters of thio-dipropionic acid, such as lauryl, stearyl, tetradecyl or tridecyl sulphuric acid, sulphur-based benzoic acid The zinc salt, dibutyldithiocarbamate, the octadecyl disulfide 'pentaquata _ _ _ _ 】 Such as melamine, polyvinylpyrrolidine

Ketone, dicyandiamide, second stone: "· So A- propyl cyano urate, urea derivative, hydrazine derivative, amine, poly urethane, flat face ethyl amide, higher carbon The metal and salt test of several fatty acids are now. i is sparse, such as calcium stearate, zinc stearate, 廿23 200914512, magnesium hard citrate, sodium ricinate, potassium palmitate, pyroic acid锑 or Jiao catechu acid. For example, inorganic substances such as talc, metal oxides, for example, cerium oxide or oxidized towns, preferably acid-filled metal acid salts, carbonated or sulfated salts; organic compounds such as mono- or poly-reactive acid and salts thereof; Di-tertiary butyl benzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate, polymeric compounds such as ionic copolymers (ionics). In particular, 1 ' 3 · 2 ' 4-bis (3' ' 4'-dimethylidene) sorbitol, 1,3: 2,4_-(p-methyldibenzylidene) sorbitol and hydrazine, 3: 2,4_bis (benzylic) sorbitol. ΙΙιΑ_fillers and reinforcing agents_, such as calcium carbonate, silicate, glass fiber, glass beads, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour, and others Natural product powders and fibers, synthetic fibers. Jg: other additives such as plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow improvers, optical brighteners, fire retardants, antistatic agents, blowing agents. 13. Other benzo ketones and ρ 引 p full _, such as those disclosed in R Xi 4,325,863; US 4,338,244; US 5,175,312; US 5 '216,052; ILS 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-43I6876; EP-A-0589839 or EP-A-0591102, or 3-[4-(2-Ethyl) Oxyethylethyl)phenyl]-5 ' 7-di-t-butylbenzopyran-2-one, 5,7·di-second-butyl-3-[4-(2- Stearyl ethoxyethoxy) base benzophenone σ nan-2-ketone ' 3 ' 3 '- bis [ 5 ' 7-di-tri-butyl _ 3 _ (4_[2_ 24 200914512 Ethoxy]phenyl)benzophenone cough phase], 5,7-di-third, (4-ethoxyphenyl)benzofuran phase, 3·(4_ethyloxy group, base group) 3-basic)-5'-7-di-t-butylbenzo benzoate m 3_(rodyl + pentyloxyphenyl)_5,7•di-t-butylbenzo-dimethyl 3 -(3,4-dimethylphenyl)_5,7_ 2·鲷, 丨-(2 fluorenyl-second-butylbenzofuran-2-oxime, preferably another additive such as light stabilizer, static electricity Agents. Just and/or anti-r "Γ2), (called) and other additives selected as leaking compounds: 疋Polypropylene-based thermoplastic polymer makes anti-oxidation, heat = induction (4). The special agency makes it possible to make (4) more: the line two-motion rate is lower than 20, and the poly-propene helmet is formed into a < The excellent function of the basic thermoplastic polyoxidant. The anti-polypropylene-based thermoplastic polymer of N. sylvestris can be prepared by the following methods in particular. Method, and a) Free radical polymerization method (usually under Korean and high temperature) b In the presence of catalyst, the catalyst is usually

Vh, VTK -t· Λ/ΤΤΤ The second periodic table IVb,

Vb VIb or Group VIII metal. Those gold-based or ligands such as oxides, and chemical groups have: more than 4 kinds: 栌 ^ ^ -η, Λ. ping, ester, ether, amine, alkyl, alkenyl and/or aryl, It can be π _ or human 铋 $ 炎ττ目# 疋 position. Such metal sigma is not supported by carriers or fixed to the carrier... Sichuan, the warfare body is fixed, for example, to activated magnesium hydride, titanium (III) titanium oxide, aluminum oxide or oxidized, The catalyst is soluble or unsuitable in the polymerization medium. The catalyst may be active in the polymerization of Putian sheep, or may be further used as an activator, for example, using a metal-free telluride, a metal alkyl 25 200914512: compound, metal alkyl oxide or metal alkyl ring For the periodic table! a, Ha and / or service metal. , tongue, this ^, for example, H (four) ΑΛ 2 agent can be improved, β ph.n. S 兀 兀 醇 文 文 文. Such catalyst systems are generally referred to as V 一 ' a VPS, Standard 〇 il Indian ' Ziegler (- sodium tower), TNZ (du), metallocene or unit catalyst (SSC). An illustrative example of such a polypropylene-based thermoplastic polymer is a mixture of a mixture of a woman and a polyisobutylene and a mixture of polypropylene and polyethylene (e.g., pp/hdpe pp/ldpe). Copolymers of mono- and di-olefins with each other or with other vinyl monomers such as acetamidine/propylene copolymer, propylene/butyl dilute copolymer, propylene/isobutyl copolymer, propylene/butadiene Alkene copolymers, hexenes and hydrides, such as dihexyl, dicyclopentadiene or ethylene borneol 2: mixtures of such copolymers with each other or with the polymers described above, such as polypropylene - Ethylene/propylene copolymer. I.- Another object of the invention is therefore a composition comprising "a poly(tetra)-based thermoplastic polymer which is susceptible to oxidative, thermal or photoinduced degradation and 11) at least one component (4), (b) and (4) Mixtures. The efficacy of the novel mixture against oxidation or thermal degradation is specifically mentioned, in particular under the action of heat occurring during the processing of thermoplastic materials. The mixtures according to the invention are therefore particularly suitable for the action of stabilizers. Ingredients (a), (b) and (c), and if desired, additional additives, such as those typically described above, will preferably be added to the polypropylene-based thermoplastic polymer to be formulated, at a concentration of 〇〇〇1 to 5%, 26 200914512 ♦ Cars are good 0 01 to 5 /. 'Typical 〇〇丨 to 1%, based on the weight of the material. Better, ingredients (4), (b) and (4) And, if desired, additional binders, such as those typically described above, will preferably be incorporated into a polypropylene-based thermoplastic polymer to be stabilized at a concentration of 0.05 to 0.5% 'e. % to the material The weight of the builder is based on, for example, 〇·〇1 to 1% by weight based on the total weight of the stabilized polypropylene-based thermoplastic polymer. In addition to ingredients (1) and (ii) In addition, the preferred composition of the step further comprises a group consisting of (4) free % stabilizer and/or acid scavenger. Particularly preferred acid scavengers are, for example, carboxylates such as stearin. Calcium acid, zinc stearate or octanoic acid or metal oxide. Further additives which are of interest in the compositions of the invention are higher fatty acid or alkaline earth metal salts of lactic acid, such as calcium stearate, calcium lactate or stearin _ 2 - Lactic acid feeding. It should be understood that the words calcium lactate or stearin _ 2 _ calcium lactate are those compounds which are not disclosed in U.S. Patent No. 4,366,280. The calcium lactate is described in, for example, The Merck. Index, Eieve Magnetic Edm〇n, 1683, p. 254 (1989). A useful description of the terms of stearin 醯 2_calcium lactate can be found, for example, in The Merck Index, Eleventh Edition, 1711, p. 257 (1989). Such as the conventionally commercialized compounds are for example As a food additive, the compounds are available from American PATCO Polymer Additives Division, Kansas City, USA under the trade name Pationic 1230 (RTM) (calcium lactate); Pati〇nic 1240 (RTM) (calcium lactate and calcium hydroxide) Mixture); Xianyu "ο 27 200914512 ) (stearin octalactic acid per liter; 卩chuan. This 940 (rtm) lactic acid and mixture of hydrogen peroxide dance); plus. (10) Di-· Qi, stearin-2-lactic acid dance and a mixture of gas oxidation). (() 劁 特 佳 佳 A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A For the traditional stabilizer combination of processing polymeric organic materials such as polyolefins into corresponding molded articles, it is recommended to use (iv) anti-= organic phosphite or phosphonite agent # secondary anti-rolling agent based on bran 9 The combination of c'i materials and methods 'Many of the dilute hydrocarbon processing agents must be operated above about the "temperature range." Including the ingredients (4) [tocopherol compound processing (4) is particularly suitable for high temperature applications, especially above the fan. Technical materials and molded articles, for example based on polypropylene: ... plastic polymer based on 'for example pipelines and their technical variables (assembly), can be: high yield and less defective manufacturing Another advantage of the stabilizer mixture of ingredients (4), (8) and (4) is that it can be used in very small amounts, resulting in less total antioxidant concentration than conventional stabilizer mixtures. For example, using low concentrations of ingredients (c ) [Best of 6%, based on the total weight of ingredients 0), (7) and: c)] reduce the total stabilizer concentration in, for example, polypropylene-based thermoplastic polymers by about three parts_ , which simultaneously represents an economic advantage. Injury (a) (b) and (c) and, if appropriate, additional additives, are incorporated into polypropylene-based thermoplastic polymers according to conventional methods, for example in seven or during 'Or by applying a solution of the stabilizer mixture or suspending 28 200914512 to a thermoplastic polymer based on polypropylene, if necessary to evaporate the solvent. Ingredients (a), (b) and (c) and, if appropriate, additional additives The stabilizer mixture may also be added to the thermoplastic polymer to be stabilized to form a masterbatch. The invention therefore also relates to a parent mixture composition comprising the component (a) And (b) and (c) and optionally additional additives as described above and a thermoplastic material which is the same as or compatible with the polypropylene polymer to be stabilized. Preferably, the parent material The composition of the mixture comprises from 1 Torr to 80 °% by weight of the thermoplastic material. - The stabilizer mixture comprising components (a), 00 and (c) and, if appropriate, additional additives may also be before or during the polymerization. Or adding 0 before the cross-linking. The stabilizer mixture containing ingredients (a), (b) and (4) and, if appropriate, additional additives may be incorporated in pure form or encapsulated in wax, oil or polymer. A polypropylene based thermoplastic polymer.

A stabilizer mixture comprising ingredients (a), (b) and (C) and, if appropriate, additional additives can be sprayed onto the polypropylene-based plastic polymer to be cured. This mixture can be used to dilute other additives (e.g., additives) or refineries thereof so that the nozzle-coated mixture can be sprayed with the additives to be stabilized with polypropylene: plastic polymer . By spraying during the deactivation of the polymerization catalyst, it is possible, for example, to use the deactivated vapor for spraying. For example, 'when a thermoplastic polymer based on polypropylene:: is polymerized to contain a mixture of X a / \ less than 3 (3), (8) and (4) and, if appropriate, a stabilizer mixture of 29 200914512 It is advantageous to apply the application method. Polypropylene-based thermoplastic polymers that are dyed in this manner can be used in a wide variety of forms, such as films, fibers, tapes, molding compounds or profiles, or for surfaces. Coated binder, especially powder coating, adhesive or cement. A polypropylene-based thermoplastic polystyrene that is stabilized in this manner is used in a very wide range of forms, in particular in the form of thick layers of polypropylene; in the form of tantalum articles, which are in continuous contact with the extract; For liquid or emulsion roads, membranes, fibers, civil films, tapes, sections or towers. The polypropylene-based thermoplastic polymer composition of the present invention can be advantageously used to prepare articles of various shapes, examples of which are: ▲ 1) / wording device 'marine application, floating dock, buoy, deck; Kayak, paddles and plastic wood for beach reinforcement. I-2) Automotive applications 'especially bumper, instrument panel, battery, front and rear lining: molded components under the car cover, cap rack, trunk lining, inside 4 2: Wang: capsule covering, electronic molding Equipped with (light), instrument panel pane solid glass: lamp glass, instrument panel, external lining, car interior and car: lamp, know the car's backlight, stop light, internal and external finishing, door panel, oil phase 'glazed front side' rear window 'seat backing, outer panel, f edge, cross-section extrusion for sealing, cladding, pillar cladding, chassis components, = system: fuel filter / transition, tank, Fuel tank, car body side visor car roof, exterior mirror, internal finishing, pieces, front: module, glass, key, brake system, luggage/top frame;; component seal, side impact protection, sound insulation material / Insulation and roof. 30 200914512) The road father's device, especially the number of notices, the road signs, the warnings, the horns, the medical box, the helmet, the tires. The device is used for aircraft, railway, car (car, locomotive) (including smear), for the application of aviation applications. <Devices, particularly rockets and satellites, such as 16) for construction and design, 'mining applications, silencer-type cakes, shelters and shelters. t system 'brain', = 7 boxes and covers and electronic / electrical devices (personal batteries, satellite snow, printers 'television, audio and video devices), flower TV discs and panel devices. I 2) For the application of other materials such as steel or textile. 11-3) For electronic workers, computer plugs, electronics and devices, especially plug insulation, especially materials for Beko storage, such as wafers, check cards or credit cards. Electric benefit, leather stove: bun utensils 'especially washing machine' clothes dryer, oven (microwave oven), dishwasher, juice machine and electric bucket. Machine grilled phase (micro 仏 5) lamp cover (such as street lights, lampshades). Π-6) Wire and cable should be used for: (+ conductor, insulation and electric galvanic sleeve). Electronic components package, semi-conductive ice phase, heating device 'air conditioner, ττ body' coffee machine and vacuum cleaner. HI-1) Technical objects Spacer, screw, 蝉# 歹1 such as cogwheel (gear), slide accessory, 磾 nail 'handle and handlebar. ΙΙΙ-2) rotor blades, ventilators and windmill blades 'solar installations, tour 31 200914512 swimming pool, swimming pool cover, pool interior, pond lining, wardrobe, wardrobe, partition wall, _ WallS, folding wall, blinds (eg roUer shUtters ), the connection between assembly, piping, kits and conveyor belts. M-s) Hygiene items, especially showers, toilet seats, lids and wash basins. ΠΙ-4) Hygiene items, especially diapers (babies, adult incontinence), female surnames, shower curtains, brushes, tweezers, buckets, mobile galleries, toothbrushes and potty. ΠΙ-5) Pipeline (interlaced or non-interlaced), water supply, waste water and chemicals, power supply line and electric shock protection pipeline 'for gas, oil and sewage pipelines, drains, sewer pipes and drainage system. ΠΙ-6) Profile and side of any geometric shape (window glass). ΠΙ-7) Glass substitutes, especially extruded sheets, used for glazing on buildings (single-walled, double-walled or multi-walled), aircraft, schools, extruded sheets, for glazing windows of buildings Membrane, train, transport, sanitary items and greenhouses. , ΠΙ-8) board (wall, chopping board), extrusion coating (photo, sterile aluminum case and pipe coating) 'mantle, wood substitute, plastic wood, wood composite, wall, surface, furniture, decoration Foil, floor coverings (internal and external applications), flooring, grooved slabs and tiles. " III-9) Intake and exhaust manifolds. III-10) Cement-, concrete-, composite application and covering, side and laminate, handrails, barriers, kitchen benches, roofs, roofing sheets, tiles and water bags. Mouth IV-1) Plate (Wall 'Chopping Board), Plate, Artificial Turf, Artificial Grass, Transportation 32 200914512 Moving ring artificial cover (sports), sports field ring artificial floor (sports) and tape. IV-2) woven fabric continuous and staple fiber, fiber (carpet/hygiene items/ceiling cloth/single filament, filter; wipe/curtain (shading)/medical application), integral fiber (applications such as robes/protective clothing) ), net, gown, cable, wire, cable, thread, safety seat belt, clothing, underwear, gloves, boots, rubber boots, + body underwear, 〉 yong clothing, sportswear, umbrella (parasol, sunshade) , descending - umbrella flying umbrella, sail, balloon silk", camping items, tents, air beds, sunbeds, bags and bags. IV-3) Membrane, insulation, covering and roof sealing, tunnel, garbage dump, pond' Wall roof membrane, civil film 'pool', curtain (shading), sunshade, canopy, canopy 'wallpaper, food packaging (elastic and sturdy), medical packaging (elastic and sturdy), airbags / seat belts, handrails and Back to head, carpet, center console, dashboard, driving M cockpit, door, overhead console module, door panel, car roof, inside a lighting 'interior mirror' shelf, rear luggage cover, Seat, power column, private Recognize .., Α,,, \ Power wheel, textiles and cabin trim. V) Membrane (packaging, garbage dump 'stacking, agriculture and gardening, greenhouse cover, along with 'black pasture'), package, swimming pool, waste Bags, wallpapers, stretch film, Raffia tree fiber, desalting membranes, batteries and connectors. VM) Food stacking and contract farming (elastic and sturdy), bottles. VI_2) Storage systems such as boxes (scorpions), luggage, boxes , household boxes, trays, racks, tracks, crawlers, screw boxes, parcels, cans. VI-3) g, injection needles, medical waste blue and waste boxes, waste bags, :: two in any container of transport, Dust box, bin Uners, loading wheel 33 200914512 , · Dustbin, general container, water / used water / chemical / gas / oil / gasoline / diesel tank; tank liners, boxes, crates 'battery box , battery boxes, medical devices such as pistons, eyeglass applications, diagnostic devices 'and for medical blister filling. VII_1) extrusion coating (photo paper, tetrapack, pipe coating), any kind of household items (for example, Appliance, thermos/clothing hanger), fixed System, such as plugs, wires and cable clamps, clamps, locks, locks, snap_cl〇SUres. VII_2) Supports for leisure time such as sports objects and fitness equipment, gymnastics mats 'ski shoes, roller skates, snowboards, big Foot, sports surface (eg tennis ball); spiral locks, stoppers, caps and cans. VII-3) General furniture, foaming objects (tweezers, shock absorbers), foams, sponges 'rags, mats, garden chairs, playground seats, tables, benches, toys, building kits (boards/numbers/balls), playrooms, slides and toy cars. VII-4) Optical and magnetic data storage materials. C, VII~5) Kitchenware (eat, drink, cook, store). , VII-6) CD, cassette and video cassette; DVD electronic items, any kind of office supply (ballpoint pen, stamp and stamp pad, mouse, shelf, track) 'bottles of any size and capacity (beverage, detergent, Includes perfumes for cosmetics, as well as adhesive tape.

Vn-7) Footwear (shoes/sole), shoe lasts, ah s, adhesives, structural agents, food containers (fruit, vegetables, meat, fish), synthetic paper, bottles & extinction, benches, man-made Joint (human), printed board (soft printing), printed electricity 34 200914512 % road board 'and display technology. VII-8) Filled polymer device (talc, chalk, real earth (local soil)' ash, pigment, carbon black, titanium dioxide 'mica, nanocomposite, dolomite, silicate, glass, Asbestos). Accordingly, another embodiment of the present invention is directed to a shaped article, particularly a film, tube, section, bottle, tank or container comprising the above composition, and the fiber strand is preferably a film. This film can be prepared as a blown film, cast film or coated by extrusion. The best one is a multilayer film. Another specific example of the invention relates to a molded article comprising the composition as described above. The molding is particularly by injection, blow molding, compression, rotational molding or gel molding or extrusion. The invention also relates to a method for the oxidation, thermal or photoinduced degradation of a polypropylene-based thermoplastic polymer comprising incorporating or applying at least one of the ingredients (a), (b) and (c) a mixture. Similarly, a preferred embodiment of the present invention is the use of a mixture of ingredients (&), (b) and (c) as a female formulation, particularly a process stabilizer (thermal stabilizer) for polypropylene. Based on thermoplastic polymers, it resists oxidation, heat or light induced degradation. ... a preferred mixture of components (a), (b) and (c) as stabilizers and a method of stabilization is as described for the composition comprising a thermoplastic polymer based on polypropylene. [Embodiment] The following examples further illustrate the invention. Parts or percentages are by weight. Re-extruding poly-ene (pp) 又 35 200914512 3·〇 kg unstabilized polypropylene homopolymer (pp) powder with 0.02% calcium stearate, ο., /. dHT 4A (RTM) (Kyowa Chemical Industry Co., Ltd. [Mg4 5Al2(0H)13C03.3.5 H20]) and the additives tested were dry blended. Then, the blend is in a twin-screw extruder

Bemorff (RTM) (ZSK 25, L/D=46) is extruded at a temperature of up to 230 °C. This extrudate was cooled and extracted via a water bath and then granulated. The granules were repeatedly extruded at 260 ° C in a single screw extruder Gattfert L/D 25 . After the first '3rd and 5th passes through the extruder, the melt flow index (MFI) [measured according to ISO 1133] and the yellowing index (YI) [determined according to ASTM D 1 925] were measured. The results are summarized in Table}-4. Table 1: Stability of the stabilizer composition (formulation) _◦/〇 formulation Irganox 1010 (RTM) Irgafos 168 (RTM) Irganox E 201 (RTM) Aa) 50 50 — Ba) 33.3 66.7 One Ca) 20 80 — Db 31.3 62.7 6 Eb) 47 47 6 Table 2: Example Formulation MFI 1 st MFI 3rd MFI 5th YI 1 st YI 3rd YI 5th 1 aa) 0.15% A 3.53 4.31 5.24 3.77 4.08 4.38 lba) 0.15% B 3.57 4.28 5.03 3.83 4.10 4.41 lca) 0.15% C 3.61 4.42 5.35 3.66 3.84 4.09 ldb) 0.15% D 3.12 3.47 3.82 4.04 4.23 4.40 leb> 0.15% E 3.24 3.52 3.88 3.80 4.1 1 4.50 36 200914512 Table 3: Example formulation MFI MFI MFI YI YI YI 1st 3rd 5th 1 st 3rd 5th lfa) 0.10% A 4.50 5.40 7.30 2.80 3.00 3.30 iga) 0.10% B 4.60 5.50 7.00 2.80 3.10 3.40 lha) 0.10% C 4.60 5.70 7.40 2.60 2.80 3.00 lib) 0.10% D 3.31 3.79 4.51 3.81 4.17 4.34 ljb) 0.10% E 3.28 3.90 4.66 3.78 3.98 4.36 Table 4: Example formulation MFI MFI MFI YI YI YI 1 st 3rd 5th 1st 3rd 5th laa) 0.15% A 3.53 4.31 5.24 3.77 4.08 4.38 lba) 0.15% B 3.57 4.28 5.03 3.83 4.10 4.41 lca) 0.15% C 3.61 4.42 5.35 3 .66 3.84 4.09 lib) 0.10% D 3.31 3.79 4.51 3.81 4.17 4.34 lib) 0.10% E 3.28 3.90 4.66 3.78 3.98 4.36 a) Comparative Example / Formulation b) Examples / Formulations of the Invention [Simple Description] Benefit 4 [Main component symbol description] Benefit 37

Claims (1)

200914512, X. Patent application scope: The present invention relates to a polypropylene-based thermoplastic polymer composition comprising a) at least one compound of the formula I, H, C h3c· HO H3C, Lh3c VCH, CHr-CHr-C—〇—CH; , CH, 〇II -C (i) b) at least one compound of the formula -P (II) ^ and c) at least one tocopherol compound in which the component (c) is present in an amount of from 0.0001 to 20%' based on the total weight of the components (a), (b) and (c). 2. According to the mixture of claim 1 of the scope of application, wherein the weight ratio of the component (^ to component (b) is 2:1 to 1:4. 3. According to the mixture of the first application of the patent scope, component (c) Compound of formula III 38 200914512 • R, (ΙΠ) where R] is —(CH. )r?nr(cH2)rcH-(cH3)2, 0 II C—R -CHrCH: -s-r3 R2 is a C7-C3G alkyl group, and R3 is a CrC3 decyl group. a mixture of the items, wherein R is 2) 3 ?(CH2)3-cH_(CH2)_CH_(CH3)2 〇4. According to the scope of the patent application, according to the patent application, the mixture of the first item In addition to the bismuth (4), (8) and (4), additives are also included. Ingredients 6 · According to the scope of the patent application, a mixture of 5 c-targets, including a light stabilizer as an external additive, sounds ‘M S text remover and / or antistatic agent. a composition comprising 0 a polypropylene-based thermoplastic polymer which is susceptible to oxidation, thermal or photoinduced degradation, and Π) a component (&) according to the scope of claim patent ^)和(^混混39 200914512 A mixture of one of the ingredients (a), (b) and (c) 8. The composition according to item 7 of the scope of the patent application, wherein the component (u) is present in an amount of 0.001 to 5 %, based on the weight of the ingredients. 9. According to the composition of claim 7 of the scope of the patent, in addition to the ingredients (1) and (ii), the additive is also included. 10. The parent mixture composition, including the patent application a stabilizer mixture of the first item and a thermoplastic material which is the same as or compatible with the polypropylene polymer to be stabilized. U. The parent mixture composition according to claim 10 of the patent application, The thermoplastic material is included in an amount of from 10 to 80% by weight. 12. A shaped article comprising the mixture according to claim 1 of the patent application. 13. - A polypropylene-based thermoplastic polymer is resistant to oxidation, heat or light Induced drop The method of the invention comprises the incorporation or application of at least one mixture according to the scope of claim 1 of the patent application. 14. - the use of the mixture according to the scope of claim patent i. The base thermoplastic polymer is resistant to oxidation, heat or light induced degradation.