• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    (A) hindered amine compound, and (B) a polar residue-containing polymer (A): (B) in a weight ratio of 20: 1 to 1:20, However, (1) component (B) is different from component (A), and does not contain the group of following general formula (I) or (II), and (2) Component (B) is different from the polymer having acidic hydrogen atoms, stabilizer mixture: (I) (II) Wherein G is hydrogen or methyl and G 1 and G 2 are independently of each other hydrogen, methyl or combined to be substituent = 0.
    公开号:KR20020075922A
    申请号:KR1020027010787
    申请日:2001-02-15
    公开日:2002-10-07
    发明作者:구구무스프랑소와스
    申请人:시바 스폐셜티 케미칼스 홀딩 인코포레이티드；
    IPC主号:
    专利说明:

    Stabilizer mixtures for polyolefins
    [2] Stabilizer mixtures containing two hindered amine compounds are for example EP-A-80 431, EP-A-252 877, EP-A-709 426, EP-A-723 990, EP-A- 728 806, GB-A-2 301 106, EP-A-741 163 and EP-A-754 723.
    [3] US-A-5 643 985 relates to stabilization of recycled plastics, and EP-A-220 897, US-A-5 475 041 and BE-A-775 151 disclose stabilization of polyolefins.
    [1] The present invention relates to stabilizer mixtures containing hindered amine compounds and polar residue containing polymers, to the use of such mixtures to stabilize polyolefins from degradation due to light, heat or oxidation and thus stabilized polyolefins.
    [4] The present invention,
    [5] (A) hindered amine compound, and
    [6] (B) a polar residue-containing polymer (A): (B) in a weight ratio of 20: 1 to 1:20,
    [7] However, (1) component (B) is different from component (A), and does not contain the group of following general formula (I) or (II), and
    [8] (2) Component (B) relates to a stabilizer mixture characterized by being different from a polymer having an acidic hydrogen atom:
    [9]
    [10]
    [11] In the above formula,
    [12] G is hydrogen or methyl, and
    [13] G 1 and G 2 are independently of each other hydrogen, methyl or combined to be substituent = 0.
    [14] Polymer having an acidic hydrogen atom means a polymer having a functional group such as carboxyl group, sulfo group, phospho group and the like. Component (B) according to the invention does not comprise a polymer with acidic hydrogen atoms described in EP-A-220 897.
    [15] The weight ratio of component (A): (B) is preferably 15: 1 to 1:15, in particular 10: 1 to 1:10, such as 5: 1 to 1: 5, 3: 1 to 1: 3, 5: 1 to 1: 1, 4: 1 to 1: 1, 3: 1 to 1: 1 or 2: 1 to 1: 1. 1: 1 weight ratio is particularly preferred.
    [16] The steric amine (component (A)) is preferably a compound containing at least one group of formula (I) or (II):
    [17] (I)
    [18] (II)
    [19] In the above formula,
    [20] G is hydrogen or methyl, and
    [21] G 1 and G 2 are independently of each other hydrogen, methyl or combined to be substituent = 0.
    [22] More detailed examples of sterically hindered amines are as described in (a ') to (i') below.
    [23] (a ') A compound of formula (la):
    [24]
    [25] In the above formula,
    [26] n 1 is a number from 1 to 4, G and G 1 are independently of each other hydrogen or methyl,
    [27] G 11 is hydrogen, O. , Hydroxyl, C 1 -C 18 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 7 -C 12 aralkyl, C 1 -C 18 alkoxy, C 5 -C 8 cycloalkoxy, C 7 -C 9 phenylalkoxy, C 1 -C 8 alkanoyl, C 3 -C 5 alkenoyl, C 1 -C 18 alkanoyloxy, glycidyl or a group of the formula -CH 2 CH (OH) -Z , Z is hydrogen, methyl or phenyl,
    [28] G 11 is preferably H, C 1 -C 4 alkyl, allyl, benzyl, acetyl or acryloil, and
    [29] G 12 is, when n 1 = 1, hydrogen, C 1 -C 18 alkyl, cyanoethyl, benzoyl, glycidyl, aliphatic, cycloaliphatic, aromatic aliphatic, with or without intermediate oxygen, at least one oxygen atom, Monovalent radicals or monovalent silyl radicals of unsaturated or aromatic carboxylic acids, carbamic acids or phosphorus-containing acids, preferably radicals of aliphatic carboxylic acids having 2 to 18 carbon atoms, radicals of cycloaliphatic carboxylic acids having 7 to 15 carbon atoms or 3 to Radicals of α, β-unsaturated carboxylic acids having 5 carbon atoms or radicals of aromatic carboxylic acids having 7 to 15 carbon atoms, each carboxylic acid may be substituted by 1 to 3 -COOZ 12 groups at aliphatic, cycloaliphatic or aromatic moieties Z 12 is H, C 1 -C 20 alkyl, C 3 -C 12 alkenyl, C 5 -C 7 cycloalkyl, phenyl or benzyl,
    [30] G 12 is C 2 -C 12 alkylene if n 1 = 2; C 4 -C 12 alkenylene; Xylylene; Divalent lidals of aliphatic, cycloaliphatic, aliphatic or aromatic dicarboxylic acids, dicarbamic acids or phosphorus-containing acids; Or divalent silyl radicals; Of radicals of aliphatic dicarboxylic acids having 2 to 36 carbon atoms, or of cycloaliphatic or aromatic dicarboxylic acids having 8 to 14 carbon atoms or of aliphatic, cycloaliphatic or aromatic dicarbamic acids having 8 to 14 carbon atoms Is a radical, each dicarboxylic acid may be substituted by one or two -COOZ 12 groups at an aliphatic, cycloaliphatic or aromatic moiety,
    [31] G 12 is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, a trivalent radical of an aromatic tricarbamic acid or a phosphorus-, if n 1 = 3, which may be substituted by —COOZ 12 groups at an aliphatic, cycloaliphatic or aromatic moiety; A trivalent radical of the containing acid or a trivalent silyl radical, and
    [32] G 12 is a tetravalent radical of aliphatic, cycloaliphatic or aromatic tetracarboxylic acid if n 1 = 4.
    [33] The aforementioned carboxylic acid radicals each mean a radical of the formula-(CO) x R, wherein x has the same meaning as n 1 and the meaning of R arises from the above definition.
    [34] Alkyl having up to 20 carbon atoms is for example methyl, ethyl, n-propyl, n-butyl, secondary butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n -Undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
    [35] C 3 -C 8 alkenyl G 11 is for example 1-propenyl, allyl, metalyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl or 4-tertbutyl-2-butenyl Can be.
    [36] C 3 -C 8 alkynyl G 11 is preferably propargyl.
    [37] C 7 -C 12 aralkyl G 11 is phenethyl, in particular benzyl.
    [38] C 1 -C 18 alkoxy G 11 is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dode Siloxy, tetradecyloxy, hexadecyloxy and octadecyloxy. Preference is given to C 6 -C 12 alkoxy, in particular heptoxy and octoxy.
    [39] C 5 -C 8 cycloalkoxy G 11 can be, for example, cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy. Preference is given to C 5 -C 8 cycloalkoxy, in particular cyclopentoxy and cyclohexoxy.
    [40] C 7 -C 9 phenylalkoxy is for example benzyloxy.
    [41] C 1 -C 8 alkanoyl G 11 is for example formyl, propionyl, butyryl, octane oil, but is preferably acetyl and C 3 -C 5 alkenoyl G 11 is especially acrylic oil.
    [42] C 1 -C 18 alkanoyloxy G 11 is for example formyloxy, acetyloxy, propionyloxy, butyryloxy, valeryloxy, lauroyloxy, palmitoyloxy and stearoyloxy.
    [43] Examples of some G 12 radicals are as follows.
    [44] If G 2 is a monovalent radical of a carboxylic acid, for example, an acetyl, caproyl, stearoyl, acryloil, methacryloyl, benzoyl or β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl radical to be.
    [45] If G 12 is a monovalent silyl radical, for example, it is a radical of the formula- (C j H 2J ) -Si (Z ') 2 Z ", wherein j is an integer ranging from 2 to 5 and Z' and Z" are independently C 1 -C 4 alkyl or C 1 -C 4 alkoxy.
    [46] If G 12 is a divalent radical of dicarboxylic acid, for example malonyl, succinyl, glutaryl, adipoyl, subveroyl, sebacoyl, maleoyl, itaconyl, phthaloyl, dibutylmalonyl, dibenzylmalo Nilyl, butyl (3,5-di-tert-butyl-4-hydroxybenzyl) malonyl or bicycloheptenedicarbonyl radicals or groups of the formula:
    [47]
    [48] If G 12 is a trivalent radical of tricarboxylic acid, it is for example trimellitoyl, citryl or nitrilotriacetyl radical.
    [49] If G 12 is a tetravalent radical of tetracarboxylic acid, it is, for example, a tetravalent radical of butane-1,2,3,4-tetracarboxylic acid or a tetravalent radical of pyromellitic acid.
    [50] If G 12 is a divalent radical of dicarbamic acid, it is, for example, a hexamethylenedicarbamoyl or 2,4-toluylenedicarbamoyl radical.
    [51] Preference is given to compounds of the formula (la) in which G and G 1 are hydrogen, G 11 is hydrogen or methyl, n 1 is 2 and G 12 is a diacyl radical of an aliphatic dicarboxylic acid having 4 to 12 carbon atoms.
    [52] Examples of polyalkylpiperidine compounds of this type are the following compounds:
    [53] 1) 4-hydroxy-2,2,6,6-tetramethylpiperidine
    [54] 2) 1-allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine
    [55] 3) 1-benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine
    [56] 4) 1- (4-tert-butyl-2-butenyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine
    [57] 5) 4-stearoyloxy-2,2,6,6-tetramethylpiperidine
    [58] 6) 1-ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine
    [59] 7) 4-methacryloiloxy-1,2,2,6,6-pentamethylpiperidine
    [60] 8) 1,2,2,6,6-pentamethylpiperidin-4-yl β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate
    [61] 9) di (1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl) maleate
    [62] 10) di (2,2,6,6-tetramethylpiperidin-4-yl) succinate
    [63] 11) di (2,2,6,6-tetramethylpiperidin-4-yl) glutarate
    [64] 12) Di (2,2,6,6-tetramethylpiperidin-4-yl) adipate
    [65] 13) di (2,2,6,6-tetramethylpiperidin-4-yl) sebacate
    [66] 14) di (1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate
    [67] 15) Di (1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl) sebacate
    [68] 16) Di (1-allyl-2,2,6,6-tetramethylpiperidin-4-yl) phthalate
    [69] 17) 1-hydroxy-4-β-cyanoethoxy-2,2,6,6-tetramethylpiperidine
    [70] 18) 1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl acetate
    [71] 19) Tri (2,2,6,6-tetramethylpiperidin-4-yl) trimelitate
    [72] 20) 1-acryloyl-4-benzyloxy-2,2,6,6-tetramethylpiperidine
    [73] 21) di (2,2,6,6-tetramethylpiperidin-4-yl) diethylmalonate
    [74] 22) Di (1,2,2,6,6-pentamethylpiperidin-4-yl) dibutylmalonate
    [75] 23) Di (1,2,2,6,6-pentamethylpiperidin-4-yl) butyl (3,5-di-tert-butyl-4-hydroxybenzyl) malonate
    [76] 24) Di (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate
    [77] 25) Di (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate
    [78] 26) Hexane-1 ', 6'-bis (4-carbamoyloxy-1-n-butyl-2,2,6,6-tetramethylpiperidine)
    [79] 27) Toluene-2 ', 4'-bis- (4-carbamoyloxy-1-n-propyl-2,2,6,6-tetramethylpiperidine)
    [80] 28) Dimethylbis (2,2,6,6-tetramethylpiperidine-4-oxy) silane
    [81] 29) Phenyltris (2,2,6,6-tetramethylpiperidine-4-oxy) silane
    [82] 30) Tris (1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphite
    [83] 30-a) Tris (1-methyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphite
    [84] 31) Tris (1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphate
    [85] 32) Phenyl bis (1,2,2,6,6-pentamethylpiperidin-4-yl) phosphonate
    [86] 33) 4-hydroxy-1,2,2,6,6-pentamethylpiperidine
    [87] 34) 4-hydroxy-N-hydroxyethyl-2,2,6,6-tetramethylpiperidine
    [88] 35) 4-hydroxy-N- (2-hydroxypropyl) -2,2,6,6-tetramethylpiperidine
    [89] 36) 1-glycidyl-4-hydroxy-2,2,6,6-tetramethylpiperidine
    [90] 36-a-1) 1,2,3,4-tetrakis [2,2,6,6-tetramethylpiperidin-4-yloxycarbonyl] butane
    [91] 36-a-2) bis [2,2,6,6-tetramethylpiperidin-4-yloxycarbonyl] -bis [tridecyloxycarbonyl] butane
    [92] 36-b-1) 1,2,3,4-tetrakis [1,2,2,6,6-pentamethylpiperidin-4-yloxycarbonyl] butane
    [93] 36-b-2) bis [1,2,2,6,6-pentamethylpiperidin-4-yloxycarbonyl] -bis [tridecyloxycarbonyl] butane
    [94] 36-c) 2,2,6,6-tetramethylpiperidin-4-yloxycarbonyl (C 15 -C 17 alkanes)
    [95] 36-d)
    [96]
    [97] 36-e)
    [98]
    [99] (b ') A compound of formula (Ib)
    [100]
    [101] Where
    [102] n 2 is a number of 1, 2 or 3, G, G 1 and G 11 are as defined under (a '),
    [103] G 13 is hydrogen, C 1 -C 12 alkyl, C 2 -C 5 hydroxyalkyl, C 5 -C 7 cycloalkyl, C 7 -C 8 aralkyl, C 1 -C 18 alkanoyl, C 3 -C 5 Alkenoyl, benzoyl or chemical formula
    [104] It is the flag of
    [105] G 14 is hydrogen, C 1 -C 18 alkyl, C 3 -C 8 alkenyl, C 5 -C 7 cycloalkyl when n 2 = 1; C 1 -C 4 alkyl substituted by hydroxyl, cyano, alkoxycarbonyl or carbamide groups; Glycidyl, a group of formula -CH 2 -CH (OH) -Z or a group of formula -CONH-Z, Z is hydrogen, methyl or phenyl;
    [106] G 14 is C 2 -C 12 alkylene, C 6 -C 12 arylene, xylylene, —CH 2 —CH (OH) —CH 2 group or —CH 2 —CH (OH) when n 2 = 2; ) -CH 2 -ODO- group, wherein D is C 2 -C 10 alkylene, C 6 -C 15 arylene, C 6 -C 12 cycloalkylene, provided that G 13 is alkane oil, alkenoyl or If not benzoyl, G 14 may alternatively be a divalent radical or —CO— group of 1-oxo-C 2 -C 12 alkylene, aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid,
    [107] If G 14 is n 2 = 3,
    [108] Is a group of or
    [109] If n 2 = 1, G 13 and G 14 may be combined to be a divalent radical of aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.
    [110] Some examples of the radicals G 13 , G 14 and D are as shown below.
    [111] Alkyl substituents are as defined in (a ').
    [112] C 5 -C 7 cycloalkyl substituents are especially cyclohexyl.
    [113] C 7 -C 8 aralkyl G 13 is especially phenylethyl or especially benzyl.
    [114] C 2 -C 5 hydroxyalkyl G 13 is especially 2-hydroxyethyl or 2-hydroxypropyl.
    [115] C 1 -C 18 alkanoil G 13 is for example formyl, acetyl, propionyl, butyryl, octane oil, dodecane oil, hexadecane oil, octadecane oil, but is preferably acetyl, and C 3 -C 5 Alkene oil G 13 is especially acrylic oil.
    [116] C 2 -C 8 alkenyl G 14 is, for example, allyl, metallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.
    [117] G 14 as hydroxy-, cyano-, alkoxycarbonyl- or carbamide-substituted C 1 -C 14 alkyl is, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxycarbo Carbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2- (dimethylaminocarbonyl) ethyl.
    [118] C 2 -C 12 alkylene radicals are, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
    [119] C 6 -C 15 arylene substituents are, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
    [120] C 6 -C 12 cycloalkylene is especially cyclohexylene.
    [121] 1-oxo -C 2 -C 12 alkylene G 14 as is preferably the following group:
    [122]
    [123] n 2 is 1 or 2, G and G 1 are hydrogen, G 11 is hydrogen or methyl, G 13 is hydrogen, C 1 -C 12 alkyl or a formula
    [124] And when n = 1 G 14 is hydrogen or C 1 -C 12 alkyl, and when n = 2, it is C 2 -C 8 alkylene or 1-oxo-C 2 -C 8 alkylene Preferred are the compounds of (Ib).
    [125] Examples of polyalkylpiperidine compounds of this type are:
    [126] 37) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylene-1,6-diamine
    [127] 38) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) hexamethylene-1,6-diacetamide
    [128] 39) bis (2,2,6,6-tetramethylpiperidin-4-yl) amine
    [129] 40) 4-benzoylamino-2,2,6,6-tetramethylpiperidine
    [130] 41) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -N, N'-dibutyladipamide
    [131] 42) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -N, N'-dicyclohexyl-2-hydroxypropylene-1,3-diamine
    [132] 43) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) -p-xylylenediamine
    [133] 44) N, N'-bis (2,2,6,6-tetramethylpiperidin-4-yl) succinamide
    [134] 45) Bis (2,2,6,6-tetramethylpiperidin-4-yl) N- (2,2,6,6-tetramethylpiperidin-4-yl) -β-aminodipropio Nate
    [135] 46) Compounds of the formula
    [136]
    [137] 47) 4- (bis-2-hydroxyethylamino) -1,2,2,6,6-pentamethylpiperidine
    [138] 48) 4- (3-Methyl-4-hydroxy-5-tert-butyl-benzamido) -2,2,6,6-tetramethylpiperidine
    [139] 49) 4-methacrylamido-1,2,2,6,6-pentamethylpiperidine
    [140] 49-a-1)
    [141]
    [142] 49-a-2)
    [143]
    [144] 49-b) N, N ', N "-tris [2,2,6,6-tetramethylpiperidin-4-ylamino (2-hydroxypropylene)] isocyanurate
    [145] 49-c) 2- (2,2,6,6-tetramethylpiperidin-4-ylamino) -2- (2,2,6,6-tetramethylpiperidin-4-ylaminocarbonyl Propane
    [146] 49-d) 1,6-bis [N- (2,2,6,6-tetramethylpiperidin-4-yl) formylamino] hexane
    [147] 49-e)
    [148]
    [149] (c ') A compound of formula (Ic)
    [150]
    [151] In the above formula,
    [152] n 3 is a number of 1 or 2, G, G 1 and G 11 are as defined under (a '), and G 15 is C 2 -C 8 alkylene, C 2 -if n 3 = 1; C 8 hydroxyalkylene or C 4 -C 22 acylalkoxyalkylene and when n 3 = 2, G 15 is a (-CH 2 ) 2 C (CH 2- ) 2 group.
    [153] C 2 -C 8 alkylene or C 2 -C 8 hydroxyalkylene G 15 is, for example, ethylene, 1-methylethylene, propylene, 2-ethylpropylene or 2-ethyl-2-hydroxymethylpropylene.
    [154] C 4 -C 22 acylalkoxyalkylene G 15 is, for example, 2-ethyl-2-acetoxymethylpropylene.
    [155] Examples of polyalkylpiperidine compounds of this type are the following compounds:
    [156] 50) 9-aza-8,8,10,10-tetramethyl-1,5-dioxaspiro [5.5] undecane
    [157] 51) 9-aza-8,8,10,10-tetramethyl-3-ethyl-1,5-oxaspiro [5.5] undecane
    [158] 52) 9-aza-2,7,7,8,9,9-hexamethyl-1,4-dioxaspiro [4.5] decane
    [159] 53) 9-aza-3-hydroxymethyl-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxaspiro [5.5] undecane
    [160] 54) 9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,10,10-tetramethyl-1,5-dioxaspiro [5.5] undecane
    [161] 55) 2,2,6,6-tetramethylpiperidine-4-spiro-2 '-(1', 3'-dioxane) -5'-spiro-5 "-(1 ", 3" -di Oxane) -2 "-spiro-4" '-(2 "', 2" ', 6 "', 6" '-tetramethylpiperidine)
    [162] (d ') A compound of formula (Id-1), (Id-2) or (Id-3):
    [163]
    [164]
    [165]
    [166] Wherein n 4 is 1 or 2, G, G 1 and G 11 are as defined under (a '),
    [167] G 16 is hydrogen, C 1 -C 12 alkyl, allyl, benzyl, glycidyl or C 2 -C 6 alkoxyalkyl, and
    [168] G 17 is, if n 4 = 1, hydrogen, C 1 -C 12 alkyl, C 3 -C 5 alkenyl, C 7 -C 9 aralkyl, C 5 -C 7 cycloalkyl, C 2 -C 4 hydroxy Alkyl, C 2 -C 6 alkoxyalkyl, C 6 -C 10 aryl, glycidyl or a group of the formula-(CH 2 ) p -COO-Q or-(CH 2 ) p -O-CO-Q, p Is 1 or 2, and Q is C 1 -C 4 alkyl or phenyl,
    [169] G 17 is C 2 -C 12 alkylene, C 4 -C 12 alkenylene, C 6 -C 12 arylene, formula -CH 2 -CH (OH) -CH 2 -O-D if n 4 = 2; Or is a group of '-O-CH 2 -CH (OH) -CH 2-, wherein D' is C 2 -C 10 alkylene, C 6 -C 15 arylene or C 6 -C 12 cycloalkylene Formula -CH 2 CH (OD ") CH 2- (OCH 2 -CH (OD") CH 2 ) 2 -wherein D "is hydrogen, C 1 -C 18 alkyl, allyl, benzyl, C 2 -C 12 alkanes Oil or benzoyl),
    [170] T 1 and T 2 are independently of each other hydrogen, C 1 -C 18 alkyl or unsubstituted or halogen- or C 1 -C 4 alkyl-substituted C 6 -C 10 aryl or C 7 -C 9 aralkyl, or
    [171] T 1 and T 2 combine with the carbon atom to which they are attached to form a C 5 -C 14 cycloalkane ring.
    [172] Preferred are compounds of formula (Id-3).
    [173] Some examples of several variable substituents in formulas (Id-1), (Id-2) and (Id-3) are as described below.
    [174] C 1 -C 12 alkyl substituents are for example methyl, ethyl, n-propyl, n-butyl, secondary butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n- Undecyl or n-dodecyl.
    [175] C 1 -C 18 alkyl substituents are, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl in addition to the groups described above.
    [176] C 2 -C 6 alkoxyalkyl substituents are for example methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopropoxyethyl Or propoxypropyl.
    [177] C 3 -C 5 alkenyl G 17 is for example 1-propenyl, allyl, metalyl, 2-butenyl or 2-pentenyl.
    [178] C 7 -C 9 aralkyl G 17 , T 1 and T 2 are especially phenethyl or benzyl. When T 1 and T 2 combine with a carbon atom to form a cycloalkane ring, it may be, for example, a cyclopentane, cyclohexane, cyclooctane or cyclododecane ring.
    [179] C 2 -C 4 hydroxyalkyl G 17 is, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.
    [180] C 6 -C 10 aryl G 17 , T 1 and T 2 are especially phenyl or α- or β-naphthyl which is unsubstituted or substituted by halogen or C 1 -C 4 alkyl.
    [181] C 2 -C 12 alkylene G 17 is for example ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
    [182] C 4 -C 12 alkenylene G 17 is especially 2-butenylene, 2-pentenylene or 3-hexenylene.
    [183] C 6 -C 12 arylene G 17 is for example o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
    [184] C 2 -C 12 alkanoyl D ″ is, for example, propionyl, butyryl, octanoyl, dodecane oil, but is preferably acetyl.
    [185] C 2 -C 10 alkylene, C 6 -C 15 arylene or C 6 -C 12 cycloalkylene D ′ may be one of the meanings given for D, for example under (b ′).
    [186] Examples of polyalkylpiperidine of this type are the following compounds:
    [187] 56) 3-benzyl-1,3,8-tria-7-7,7,9,9-tetramethylspiro [4.5] decane-2,4-dione
    [188] 57) 3-n-octyl-1,3,8-tria-7-7,7,9,9-tetramethylspiro [4.5] decane-2,4-dione
    [189] 58) 3-allyl-1,3,8-triaza-1,7,7,9,9-pentamethylspiro [4.5] decane-2,4-dione
    [190] 59) 3-glycidyl-1,3,8-tria-7-7,7,8,9,9-pentamethylspiro [4.5] decane-2,4-dione
    [191] 60) 1,3,7,7,8,9,9-heptamethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione
    [192] 61) 2-isopropyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospyro [4.5] decane
    [193] 62) 2,2-dibutyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospyro [4.5] decane
    [194] 63) 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodisspiro [5.1.11.2] henic acid
    [195] 64) 2-butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxospyro [4.5] decane and preferably
    [196] 65) 8-acetyl-3-dodecyl-1,3,8-tria-7-7,7,9,9-tetramethylspiro [4.5] decane-2,4-dione and a compound of formula
    [197] 66)
    [198]
    [199] 67)
    [200]
    [201] 68)
    [202]
    [203] 69-a)
    [204]
    [205] 69-b) 60% by weight
    [206] And
    [207] 40% by weight Mixture of
    [208] (e ') A compound of formula (Ie)
    [209]
    [210] In the above formula,
    [211] n 5 is a number of 1 or 2, and G 18 is a group of the formula
    [212]
    [213] G and G 11 are as defined under (a '), and G 1 and G 2 are hydrogen, methyl or combined substituent = O,
    [214] E is -O- or -ND "'-,
    [215] A is C 2 -C 6 alkylene or-(CH 2 ) 3 -O-, further
    [216] x 1 is 0 or 1,
    [217] D ″ ′ is hydrogen, C 1 -C 12 alkyl, C 2 -C 5 hydroxyalkyl or C 5 -C 7 cycloalkyl,
    [218] G 19 is the same as G 18 or is one of -N (G 21 ) (G 22 ), -OG 23 , -N (H) (CH 2 OG 23 ) or -N (CH 2 OG 23 ) 2 groups,
    [219] G 20 is equal to G 18 if n 5 = 1 and n 5 = 2 is an -ED IV -E- group where D IV is C 2 -C 8 alkylene or 1 or 2-in between C 2 -C 8 alkylene comprising NG 21 -groups,
    [220] G 21 is C 1 -C 12 alkyl, cyclohexyl, benzyl or C 1 -C 4 hydroxyalkyl or a group of formula
    [221]
    [222] G 22 is C 1 -C 12 alkyl, cyclohexyl, benzyl or C 1 -C 4 hydroxyalkyl, and
    [223] G 23 is hydrogen, C 1 -C 12 alkyl or phenyl or G 21 and G 22 are combined to form a C 4 -C 5 egg
    [224] Or a C 4 -C 5 oxaalkylene, such as —CH 2 CH 2 —O—CH 2 CH 2 — or —CH 2 CH 2 —N (G 11 ) —CH 2 CH 2 —.
    [225] Some examples of some substituents in formula (Ie) are as follows.
    [226] C 1 -C 12 alkyl substituents are for example methyl, ethyl, n-propyl, n-butyl, secondary butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n- Undecyl or n-dodecyl.
    [227] Hydroxyalkyl substituents are, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.
    [228] C 5 -C 7 cycloalkyl substituents are, for example, cyclopentyl, cyclohexyl or cycloheptyl. Cyclohexyl is preferred.
    [229] C 2 -C 6 alkylene A is for example ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene.
    [230] If G 21 and G 22 are taken together and C 4 -C 5 alkylene or oxaalkylene, these are, for example, tetramethylene, pentamethylene or 3-oxapentamethylene.
    [231] Examples of polyalkylpiperidine compounds of this type are compounds of the formula:
    [232]
    [233]
    [234]
    [235]
    [236]
    [237]
    [238]
    [239]
    [240]
    [241]
    [242]
    [243]
    [244] (f ') A compound of formula (If):
    [245]
    [246] In the formula, G 11 is as defined under (a ').
    [247] Preferred examples of this type are the following compounds:
    [248]
    [249] (g ') repeat structural units are 2,2,6,6-tetraalkylpiperidinyl radicals, in particular polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly (meth) Oligomers or polymerizable compounds containing radicals such as acrylates, poly (meth) acrylamides and copolymers thereof.
    [250] Examples of 2,2,6,6-polyalkylpiperidine compounds of this type are compounds of the formula m 1 to m 14 are numbers from 2 to about 200, preferably 2 to 100, such as 2 to 50, 2 to 40, 3 to 40 or 4 to 10.
    [251] The meaning of the end groups saturating free valences in the oligomeric or polymeric compounds listed below depends on the method used to prepare the compounds. The end group can be modified after synthesizing the compound.
    [252]
    [253]
    [254] In the compounds (82-a) and (82-b), the terminal group bonded to -O- is for example hydrogen or -CO- (CH 2 ) 2 -COO-Y or -CO- (CH 2 ) 4 -COO- Is a group of Y, wherein Y is hydrogen or C 1 -C 4 alkyl and the terminal group bonded to the diacyl is for example -OY or
    [255] Is.
    [256]
    [257] In compound (83), the terminal group bonded to the amino moiety is for example
    [258] And the end group bound to the diacyl moiety can be for example Cl.
    [259]
    [260] In compounds (84-1-a), (84-1-b) and (84-2), the terminal groups bonded to the triazine residues are for example chlorine or
    [261] And groups bonded to the diamino group, for example hydrogen or
    [262] It may be a flag.
    [263] It may be advantageous to substitute the chlorine attached to the triazine with, for example, -OH or an amino group. Suitable amino groups are typically pyrrolidin-1-yl, morpholino, -NH 2 , -N (C 1 -C 8 alkyl) 2 and -NY '(C 1 -C 8 alkyl), and Y' is hydrogen or
    [264] Qi.
    [265]
    [266] In compound (85), the terminal group bonded to the 2,2,6,6-tetramethylpiperidin-4-ylamino residue can be for example hydrogen and the terminal group linked to the 2-hydroxypropylene residue is for example It may be a flag.
    [267]
    [268] In compound (86), the terminal group bonded to -O- is for example hydrogen or And the end group attached to the diacyl moiety is, for example, -OCH 3 or Cl.
    [269]
    [270] In compound (87), the terminal group bonded to -O- is for example hydrogen or And the end group bonded to the diacyl radical is, for example, -OCH 3 or Cl.
    [271]
    [272] In compound (88), the terminal group bonded to -O- is for example hydrogen or And may be a group attached to the diacyl radical such as —OCH 3 or Cl.
    [273]
    [274] In compound (89), the terminal group bonded to —CH 2 — is for example hydrogen and the terminal group bonded to an ester moiety is for example
    [275] Can be.
    [276]
    [277] In compound (90), the terminal group bonded to —CH 2 — is, for example, hydrogen and the terminal group bonded to an ester moiety is, for example,
    [278] Can be.
    [279]
    [280] In compound (91), the end group bonded to —CH 2 — may be, for example, hydrogen and the end group bonded to the amide moiety is, for example,
    [281] Can be.
    [282]
    [283] Wherein m 11 * is as defined for m 11 and the radicals R * are independently ethyl or 2,2,6,6-tetramethylpiperidin-4-yl, provided that at least 50% of the radicals R * Is 2,2,6,6-tetramethylpiperidin-4-yl and the remaining radicals R * are ethyl. In compound 91-1), the terminal group is for example hydrogen.
    [284]
    [285] In compounds (92) and (93), the end groups attached to the triazine residues are for example chlorine or in compound (92)
    [286] In groups and compounds (93)
    [287] And the terminal group bonded to the multiamino moiety is for example hydrogen or Can be.
    [288] It may be advantageous to substitute the chlorine attached to the triazine with, for example, -OH or an amino group. Suitable amino groups are typically pyrrolidin-4-yl, morpholino, -NH 2 , -N (C 1 -C 8 alkyl) 2 and -NY '(C 1 -C 8 alkyl), and Y' is hydrogen Or chemical formula
    [289] It can be the flag of.
    [290]
    [291] In compound (94), the end group bonded to the diamino moiety can be for example hydrogen and the end group bonded to -CH 2 CH 2 -is for example Can be.
    [292]
    [293] In compound 95-1, the terminal group bonded to the diamino residue may be for example hydrogen and the terminal group bonded to the diacyl residue may be for example Cl.
    [294]
    [295] Wherein R ″ is a group of formula (95-2)
    [296] Or branched And, R "is a group of the formula (95-2) or m '15 and m" 15 is a number from 0 to 200, preferably from 0 to 100, in particular 0 to 50, with the proviso that m' 15 + m "15 Is a number from 2 to 200, preferably from 2 to 100, in particular from 2 to 50. In compound 95-1, the terminal group bonded to the diamino moiety can be for example hydrogen and is bonded to the —CH 2 CH 2 — group. Terminal groups are for example halogen, in particular Cl or Br.
    [297] A compound of formula (96-I) or (96-II):
    [298]
    [299]
    [300] Wherein m 16 and m 16 * are a number from 2 to 50, such as from 2 to 25.
    [301] During the preparation, the compounds of the formulas (96-I) and (96-II) can be produced in mixtures and therefore they can be used as is. The weight ratio of (96-I): (96-II) is, for example, 20: 1 to 1:20 or 1:10 to 10: 1.
    [302] In the compounds of the formula (96-I), the end group bonded to nitrogen can be for example hydrogen and the end group bonded to a 2-hydroxypropylene radical is for example
    [303] It can be a machine.
    [304] In the compounds of the formula (96-II), the end group bonded to the dimethylene radical can be for example -OH and the end group bonded to oxygen can be for example hydrogen. The end group can be a polyether radical.
    [305] A compound of formula (96-III)
    [306]
    [307] Wherein Q 1 * and Q 2 * are independently hydrogen or C 1 -C 8 alkyl, or Q 1 * and Q 2 * combine to form a C 5 -C 11 alkylene group, variable m 16 ** Is independently a number from 1 to 50.
    [308] Other examples of polymerizable compounds are as follows:
    [309] 1) A compound of formula (97)
    [310]
    [311] Wherein G 24 , G 25 , G 26 , G 27 and G 28 are each independently a direct bond or C 1 -C 10 alkylene, G 11 is as defined under (a ′) and m 17 is Number from 1 to 50.
    [312] In compounds of formula (97), the terminal groups bonded to> C═O are for example And end groups bonded to oxygen, for example
    [313] Can be.
    [314] Two compounds are preferred:
    [315] And
    [316]
    [317] Wherein m 17 is a number from 1 to 20.
    [318] 2) a compound of formula (98)
    [319]
    [320] Wherein about one third of the radical R IV is —C 2 H 5 and the remainder And m 18 is a number from 2 to 200, preferably 2 to 100, in particular 2 to 50.
    [321] In compound 98, the end group bonded to the —CH 2 — moiety may be, for example, hydrogen and the end group bonded to —CH (CO 2 R IV ) may be, for example, —CH═CH—COOR IV .
    [322] 3) Compound of Formula (99):
    [323]
    [324] Wherein G 11 is as defined under (a '), G 29 and G 32 are each independently a direct bond or a -N (X 1 ) -CO-X 2 -CO-N (X 3 )-group , X 1 and X 3 are independently of each other hydrogen, C 1 -C 8 alkyl, C 5 -C 12 cycloalkyl, phenyl, C 7 -C 9 phenylalkyl or formula (99-1)
    [325] And X 2 is a direct bond or C 1 -C 4 alkylene, and G 30 , G 31 , G 34 and G 35 are independently of each other hydrogen, C 1 -C 30 alkyl, C 5 -C 12 cycloalkyl Or phenyl, G 33 is hydrogen, C 1 -C 30 alkyl, C 5 -C 12 cycloalkyl, C 7 -C 9 phenylalkyl, phenyl or a group of formula (99-1), and m 19 is 1 to Number of 50.
    [326] In the compound of formula (99), the terminal group bonded to the 2,5-dioxopyrrolidine ring can be for example hydrogen and the terminal group bonded to the -C (G 34 ) (G 35 )-radical is for example
    [327] Can be.
    [328] Examples of compounds of formula (99) are as follows:
    [329]
    [330]
    [331] Wherein G 11 is hydrogen or methyl and m 19 is a number from 1 to 25.
    [332] 4) A product obtainable by reacting an intermediate obtained by reacting a polyamine of formula (100a) with cyanuric chloride with a compound of formula (100b):
    [333]
    [334] In the above formula,
    [335] m '20 , m " 20 and m'" 20 are independently a number from 2 to 12, G 36 is hydrogen, C 1 -C 12 alkyl, C 5 -C 12 cycloalkyl, phenyl or C 7 -C 9 phenyl Alkyl and G 11 is as defined under (a ′). Preferred products are Chemical Abstracts-CAS No. 136 504-96-6 (Compound 100-A).
    [336] In general, the reaction product can be represented, for example, by a compound of the formula (100-1), (100-2) or (100-3). It may also be in the form of a mixture of these three compounds.
    [337]
    [338]
    [339]
    [340] The preferred meaning of formula (100-1) is as follows:
    [341]
    [342] The preferred meaning of formula (100-2) is as follows:
    [343]
    [344] The preferred meaning of formula (100-3) is as follows:
    [345]
    [346] In the above formulas (100-1) to (100-3), m 20 is preferably 2 to 20, in particular 2 to 10.
    [347] 5) Compounds of Formula (101):
    [348]
    [349] Wherein G 11 is as defined under (a '), G 37 is C 1 -C 10 alkyl, C 5 -C 12 cycloalkyl, C 1 -C 4 alkyl-substituted C 5 -C 12 cycloalkyl, Phenyl or C 1 -C 10 alkyl-substituted phenyl, G 38 is C 3 -C 10 alkylene and m 21 is a number from 1 to 50.
    [350] In the compound of formula (101), the terminal group bonded to the silicon atom may be, for example, (G 37 ) 3 Si—O— and the terminal group bonded to oxygen may be, for example, —Si (G 37 ) 3 .
    [351] The compound of formula (101) may be in the form of a cyclic compound if m 21 is a number from 3 to 10, that is, if the free valence represented by the structural formula forms a direct bond.
    [352] Examples of compounds of formula (101) are compounds of formula (101-I):
    [353] (101-I)
    [354] Wherein m 21 is a number from 1 to 20, such as from 2 to 20.
    [355] In the oligomeric and polymerizable compounds shown above, examples of alkyl are methyl, ethyl, propyl, isopropyl, n-butyl, secondary butyl, isobutyl, tertiary 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, 5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, icosyl and docosyl; Examples of cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; An example of C 7 -C 9 phenylalkyl is benzyl; Examples of alkylene are ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene and decamethylene.
    [356] (h ') A compound of formula (Ih):
    [357]
    [358] Wherein n 6 is a number of 1 or 2, G and G 11 are as defined under (a '), and G 14 is as defined under (b'), but G 14 is -CONH-Z and- It cannot be CH 2 -CH (OH) -CH 2 -ODO-.
    [359] Examples of such compounds are as follows:
    [360]
    [361]
    [362]
    [363] (i ') A compound of formula (Ii)
    [364]
    [365] Wherein the radicals G 39 are each independently of the formula (Ii-1)
    [366] Wherein G 40 is C 1 -C 12 alkyl or C 5 -C 12 cycloalkyl, G 41 is C 2 -C 12 alkylene and G 42 is hydrogen, C 1 -C 8 alkyl, -O . , -CH 2 CN, C 3 -C 6 alkenyl, C 7 -C 9 phenylalkyl, phenyl radical or substituted on a C 7 -C 9 phenylalkyl by C 1 -C 4 alkyl; Or C 1 -C 8 acyl.
    [367] Alkyl is for example C 1 -C 4 alkyl, in particular methyl, ethyl, propyl or butyl.
    [368] Cycloalkyl is preferably cyclohexyl.
    [369] Alkylene is for example ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene or hexamethylene.
    [370] Alkenyl is preferably allyl.
    [371] Phenylalkyl is preferably benzyl.
    [372] Acyl is preferably acetyl.
    [373] Examples of compounds of this type are compounds of the formula:
    [374]
    [375]
    [376] The hindered amine compounds listed above are known and can be prepared according to known methods if they are not commercially available.
    [377] Some of the preferred hindered amines are commercially available under the following trade names:
    [378]
    [379] According to an important embodiment, component (A) comprises compounds (5), (13), (14), (23), (24), (36-a-1), (36-a-2), (36 -b-1), (36-b-2), (36-d), (49-a-1), (49-a-2), (49-c), (49-d), (49 -e), (63), (65), (69-a), (81), (82), (102), (105) or (106), in particular compounds (5), (13), (14 ), (24), (49-a-1), (49-a-2) or (49-d), in particular compound (13).
    [380] According to a particularly important embodiment, component (A) comprises compounds (76), (82-a), (84-1-a), (84-1-b), (84-2), (91-1) , (92), (93), (96-I), (96-II), (97-I), (97-II), (99-I), (99-II), (99-III) , (100-A) or (101-I), especially compounds (76), (84-1-a), (84-1-b), (92), (93), (99-I), ( 100-A) or (101-I), especially compounds (76), (84-1-a), (84-1-b), (92) or (100-A).
    [381] The polymer (component (B)) having a polar group is preferably as follows:
    [382] (B-1) halogen-containing polymer,
    [383] (B-2) polymers or derivatives thereof derived from α, β-unsaturated acids,
    [384] (B-3) acrylonitrile / butadiene copolymer, acrylonitrile / alkyl acrylate copolymer, ethylene / acrylate copolymer, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide copolymer or acryl Nitrile / alkyl methacrylate / butadiene terpolymer,
    [385] (B-4) polymers derived from unsaturated alcohols and amines or acyl derivatives or acetals thereof,
    [386] (B-5) homopolymers or copolymers of cyclic ethers,
    [387] (B-6) polyacetal,
    [388] (B-7) polyphenylene oxide, or a mixture of polyphenylene oxide and another polymer, such as polyamide,
    [389] (B-8) polyurethane,
    [390] (B-9) polyamide or copolyamide,
    [391] (B-10) polyurea, polyimide, polyamide-imide, polyetherimide, polyesterimide, polyhydantoin, polybenzimidazole or polyvinylimidazole,
    [392] (B-11) polyester,
    [393] (B-12) polycarbonate or polyester carbonate,
    [394] (B-13) polysulfones, polyether sulfones or polyether ketones,
    [395] (B-14) polymers derived from aldehydes and phenols, ureas or melamines,
    [396] (B-15) dry or non-dry alkyd resin,
    [397] (B-16) unsaturated polyester resin,
    [398] (B-17) crosslinkable acrylic resin,
    [399] (B-18) Alkyd resin, polyester resin or acrylate resin crosslinked with melamine resin, urea resin, isocyanate, isocyanurate, polyisocyanate or epoxy resin,
    [400] (B-19) epoxy resin,
    [401] (B-20) cellulose or chemically modified homologous derivatives thereof,
    [402] (B-21) polyorgano siloxane,
    [403] (B-22) polyvinyl formal (PVF),
    [404] (B-23) poly (aryl-ether-ether-ketone) (PEEK), or
    [405] (B-24) Copolymers of vinyl aromatic monomers.
    [406] Examples of halogen-containing polymers (B-1) include polychloroprene, chlorinated rubber, chlorinated and brominated copolymers of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epi Chlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride / vinyl Leaden chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetal copolymer. Polyfluorohydrocarbons and polyvinyl formals are preferred.
    [407] Examples of polymers derived from α, β-unsaturated acids and derivatives thereof (B-2) include polyacrylates and polymethacrylates; Polymethyl methacrylate, polyacrylamide and polyacrylonitrile impact modified with butyl acrylate.
    [408] Examples of polymers derived from unsaturated alcohols and amines or acyl derivatives or acetals (B-4) thereof include polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, Polyallyl phthalate or polyallyl melamine as well as copolymers of these with olefins.
    [409] Examples of homopolymers and copolymers (B-5) of cyclic ethers are polyalkylene glycols, polyethylene oxides, polypropylene oxides or copolymers of these with bisglycidyl ethers.
    [410] Examples of polyacetals (B-6) include polyoxymethylene and their polyoxymethylene containing ethylene oxide as comonomers; Polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
    [411] Examples of polyurethanes (B-8) are polyurethanes derived from hydroxy-terminated polyethers, polyesters or polybutadienes and aliphatic or aromatic polyisocyanates as well as precursors thereof.
    [412] Examples of polyamides and copolyamides (B-9) are those derived from diamines and dicarboxylic acids and / or those derived from aminocarboxylic acids or the corresponding lactams, such as polyamide 4, polyamide 6, polyamide 6/6 , Aromatic polyamides derived from 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, m-xylene and adipic acid; Polyamides prepared from hexamethylenediamine and isophthalic acid and / or terephthalic acid with or without elastomers such as poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide as modifier ; And block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; Or block copolymers of the aforementioned polyamides with polyethers such as polyethylene glycol, polypropylene glycol or polytetramethylene glycol; As well as polyamides or copolyamides modified with EPDM or ABS; And polyamides condensed during processing (RIM polyamide systems).
    [413] Examples of polyesters (B-11) are polyesters derived from dicarboxylic acids and diols and / or hydroxycarboxylic acids or corresponding lactones, such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclo Block copolyether esters derived from hexane terephthalate, polyalkylene naphthalate (PAN) and polyhydroxybenzoate as well as hydroxy-terminated polyethers; And polyesters modified with polycarbonate or MBS.
    [414] Examples of aldehydes and polymers derived from phenol, urea and melamine (B-14) are phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins.
    [415] Examples of unsaturated polyester resins (B-16) are those derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents and halogen-containing variants with low flammability.
    [416] Examples of crosslinkable acrylic resins (B-17) are those derived from substituted acrylates, such as epoxy acrylates, urethane acrylates or polyester acrylates.
    [417] Examples of epoxy resins (B-19) are those derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, such as bisphenol A crosslinked with conventional curing agents such as anhydrides or amines, with or without accelerators. And diglycidyl ether product of bisphenol F.
    [418] Examples of cellulose or chemically modified homologous derivatives thereof (B-20) are cellulose acetate, cellulose propionate and cellulose butyrate, or cellulose ethers such as methyl cellulose.
    [419] Examples of copolymers of vinyl aromatic monomers (B-24) include styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, Styrene / acrylonitrile / methyl acrylate.
    [420] Particular preference is given to acrylic ester / styrene / acrylonitrile copolymers (ASA), styrene / acrylonitrile copolymers (SAN) and styrene / maleic anhydride copolymers (SMA).
    [421] Examples of vinyl aromatic monomers are all isomers of styrene, α-methylstyrene, vinyl toluene, especially all isomers of p-vinyltoluene, ethyl styrene, propyl styrene, vinyl biphenyl, vinyl naphthalene and vinyl anthracene. Suitable comonomers of these vinyl aromatic monomers are for example nitrile, maleic anhydride, maleimide, vinyl acetate and vinyl chloride or acrylic derivatives.
    [422] Component (B) is preferably (B-2), (B-4), (B-6), (B-7), (B-8), (B-9), (B-11), (B-12) and (B-13). According to a more preferred embodiment, component (B) comprises polyacrylate, polymethacrylate (PMA), polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), polyvinyl alcohol (PVA), polyvinyl acetate (PVAc), polyoxymethylene (POM), polyphenylene ether (PPE), polyurethane, polyamide 3 (PA3), polyamide 6 (PA6), polyamide 11 (PA 11), polyamide 12 (PA 12 ), Polyamide 66 (PA 66), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyacetic acid (PLA), polycarbonate (PC) or polyethersulfone (PES) or a chemical formula Aromatic aliphatic polysulfone (PSP) having a repeating unit of.
    [423] According to a more preferred embodiment, component (B) comprises polyamide (PA), acrylic ester / styrene / acrylonitrile copolymer (ASA), styrene / acrylonitrile copolymer (SAN), styrene / maleic anhydride copolymer (SMA) or polyether amide.
    [424] According to a particularly preferred embodiment, component (B) comprises polymethacrylate (PMA), polymethyl methacrylate (PMMA), polyamide (PA), polyoxymethylene (POM), acrylic ester / styrene / acrylonitrile Copolymer (ASA) or polyether amide.
    [425] Preferred stabilizer mixtures are wherein component (A) is compound di (2,2,6,6-tetramethylpiperidin-4-yl) sebacate and component (B) is polyethylene terephthalate (PET), polyamide 6 (PA 6), polycarbonate (PC), polymethacrylate (PMA) or polymethyl methacrylate (PMMA), in particular polymethyl methacrylate (PMMA), with a weight ratio of components (A) :( B) being 5 A mixture of from 1: 1 to 1: 5.
    [426] More preferred stabilizer mixtures are provided in which component (A) is a compound di (2,2,6,6-tetramethylpiperidin-4-yl) sebacate or formula
    [427]
    [428] Wherein m 4 is a number from 2 to 40 and component (B) is a mixture of polyamide (PA), polyoxymethylene (POM) or polyether amide.
    [429] A further preferred embodiment of the invention relates to a composition which further contains an organic salt of Ca, an inorganic salt of Ca, Ca oxide or Ca hydroxide as additional component (XX).
    [430] Examples of organic salts of Ca are Ca-stearate, Ca-laurate, Ca-lactate and Ca-stearoyl-lactate.
    [431] Examples of inorganic salts of Ca are CaCO 3 , CaCl 2 , CaF 2 , Ca 3 (PO 4 ) 2 , CaHPO 4 , Ca (PO 3 ) 2 , Ca 2 P 2 O 7 , CaSO 4 and CaSiO 3 .
    [432] More preferred embodiments of the present invention further contain organic salts of Zn, inorganic salts of Zn, Zn oxides, Zn hydroxides, organic salts of Mg, inorganic salts of Mg, Mg oxides or Mg hydroxides as additional components (XXX). It relates to a composition.
    [433] The organic salt of zinc or magnesium is preferably acetylacetonate or monocarboxylate having 1 to 24 carbon atoms. Particularly preferred examples are magnesium acetate, laurate and stearate, zinc formate, acetate, oenaphthalate, laurate and stearate, as well as zinc acetylacetonate and magnesium acetylacetonate.
    [434] Of particular interest are zinc acetate, magnesium stearate, zinc acetylacetonate, magnesium acetylacetonate, zinc acetate and magnesium acetate.
    [435] Inorganic salts of zinc or magnesium include carbonate-containing compounds such as Ca / Mg carbonates such as Zn-hydroxide-carbonate, Mg-hydroxide-carbonate, dolomite, such as Microdol Super (RTM) available from Micro Minerals (RTM); Or natural or synthetic hydrotalcite.
    [436] Natural hydrotalcite has the structure of Mg 6 Al 2 (OH) 16 CO 3 .4H 2 O. A typical laboratory of synthetic hydrotalcite is Al 2 Mg 4.35 OH 11.36 CO 3 (1.67) x H 2 O. Examples of synthetic products are as follows:
    [437]
    [438] Preferred synthetic hydrotalcites are ZHT-4A (RTM) and DHT-4A (RTM) available from Gyowa Chemical Industries Company (RTM) as well as L-55R II (RTM) available from REHEIS (RTM).
    [439] Stabilizer mixtures according to the invention are useful for stabilizing polyolefins from decomposition due to light, heat or oxidation. Examples of suitable polyolefins are as shown below.
    [440] 1. Polymers of monoolefins and diolpins such as polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as cycloolefins (eg Polymers of cyclopentene or norbornene), polyethylene (which may optionally be 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).
    [441] The polyolefins, ie the polymers of the monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be produced in various ways, in particular by the following method:
    [442] a) radical polymerization reaction (normally under high pressure and high temperature)
    [443] b) Catalytic polymerization using catalysts which normally comprise at least one of IVb, Vb, VIb or Group VIII metals of the periodic table. Such metals generally have one or more ligands, such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls, which may be π- or σ-coordinated. Such metal complexes may be in glass form or immobilized on a substrate (eg, active magnesium chloride, titanium (III) chloride, alumina or silicon oxide). Such catalysts may be soluble or insoluble in the polymerization medium. The catalyst can be used independently in the polymerization or additional activators (such as metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, in which the metal is an element of groups Ia, IIa and / or IIIa of the Periodic Table) Can be. The active agent can be conveniently modified with additional ester, ether, amine or silyl ether groups. The catalyst system is generally referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or cationic catalyst (SSC).
    [444] 2. 1) Mixtures of the polymers mentioned hereinafter such as polypropylene and polyisobutylene, mixtures of polypropylene and polyethylene (eg PP / HDPE, PP / LDPE) and mixtures of various types of polyethylene (eg LDPE / HDPE).
    [445] 3. Copolymers of monoolefins and diolefins with each other or with other vinyl units, such as ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and low density polyethylene (LDPE) and mixtures thereof, propylene / but-1-ene air Copolymer, propylene / isobutylene copolymer, ethylene / but-1-ene copolymer, ethylene / hexene copolymer, ethylene / methylpentene copolymer, ethylene / heptene copolymer, ethylene / octene copolymer, propylene / butadiene copolymer Isobutylene / isoprene copolymer, ethylene / alkyl acrylate copolymer, ethylene / alkyl methacrylate copolymer, ethylene / vinyl acetate copolymer and carbon monoxide and their copolymers or ethylene / acrylic acid copolymers and salts thereof ( Ionomer), as well as trimers of ethylene and propylene and dienes (eg hexadiene, dicyclopentadiene or ethylidene-norbornene) .; And mixtures of such copolymers and mixtures of such copolymers with the polymers mentioned in 1) 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 other polymers such as polyamides and mixtures thereof.
    [446] The present invention relates to a composition containing a polyolefin and a stabilizer mixture as described above and to a method for stabilizing a polyolefin from decomposition induced by light, heat or oxidation, comprising incorporating the stabilizer mixture according to the invention in the polyolefin. .
    [447] The polyolefin listed in said 1 is preferable. Particular preference is given to polyethylene and polypropylene as well as polyethylene copolymers or polypropylene copolymers.
    [448] The components of the stabilizer mixture can be added to the polyolefins to be stabilized individually or in admixture with each other. The stabilizer mixture (components A and B) is preferably present in an amount of from 0.01 to 5% by weight, in particular from 0.05 to 1% by weight, based on the weight of the polyolefin.
    [449] Component (B) is 0.005 to 1.5% by weight, 0.005 to 1.0% by weight, 0.01 to% by weight, 0.05 to 1.0% by weight, 0.05 to 0.5% by weight, in particular 0.05 to 0.2% or 0.01 to 0.2% by weight, based on the weight of the polyolefin. Present in an amount of%.
    [450] The Ca compound (component (XX)) may optionally be present in the material to be stabilized in an amount of 0.005 to 1% by weight, preferably 0.05 to 0.2% by weight.
    [451] Component (XXX) may optionally be present in the material to be stabilized in an amount of 0.005 to 1% by weight, in particular 0.05 to 0.2% by weight, based on the weight of the material.
    [452] The weight ratio of component (A) to (XX) is, for example, from 1:10 to 100: 1, preferably from 1: 5 to 5: 1, in particular from 1: 2 to 2: 1.
    [453] The weight ratio of component (A) to (XXX) is, for example, from 1:10 to 20: 1, preferably from 1: 5 to 5: 1, in particular from 1: 2 to 2: 1.
    [454] The novel stabilizer mixture or individual components may be incorporated by known methods, such as by adding to the polyolefin or optionally dissolving the solvent in the polyolefin before or during molding or by dissolving or dispersing the compound. The novel stabilizer mixture can be added to the polyolefin in the form of a masterbatch containing powders, granules or mixtures, for example in concentrations of 2.5 to 25% by weight.
    [455] If necessary, the components of the novel stabilizer mixture may each be melt mixed with each other before they are incorporated into the polyolefin.
    [456] The novel stabilizer mixture or components thereof may be added before or during the polymerization or before crosslinking.
    [457] Such stabilized materials can be used in various forms, such as films, fibers, tapes, molding compositions, binders for profiles or paints, adhesives or putties.
    [458] The stabilized polyolefins of the present invention may also further contain various conventional additives, such as:
    [459] 1. Antioxidant
    [460] 1.1. Alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6 -Di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-di-cyclopentyl-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, Nonylphenol branched straight or branched such as 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methyl-undec-1'-yl) -phenol, 2, 4-dimethyl-6- (1'-methyl-heptadec-1'-yl) -phenol, 2,4-dimethyl-6- (1'-methyltridec-1'-yl) -phenol and mixtures thereof .
    [461] 1.2. Alkylthiomethylphenols such as 2,4-di-octylthiomethyl-6-tert-butylphenol, 2,4-di-octylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6- Ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.
    [462] 1.3. Hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl 4-octadecyloxyphenol, 2,6-di-tert-butyl-hydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole , 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
    [463] 1.4. Tocopherols such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E).
    [464] 1.5. Hydroxylated thiodiphenyl ethers such as 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thio Bis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-secondary amylphenol) , 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide.
    [465] 1.6. Alkylidene bisphenols such as 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'-ethylidenebis (4,6-di-tert-butylphenol), 2,2 ' -Ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2- Methylphenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4- Methylphenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methyl-phenyl)- 3-n-dodecyl mercaptobu Ethane, ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methyl-phenyl) dicyclopentadiene , Bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis- (3,5-dimethyl- 2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) -propane, 2,2-bis (5-tert-butyl-4-hydroxy-2- Methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.
    [466] 1.7. O-, N- and S-benzyl compounds , for example 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxy-dibenzyl ether, octadecyl-4-hydroxy- 3,5-dimethylbenzylmercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris (3,5-di-tert-butyl-4- hydroxybenzyl) amine, Bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5 Di-tert-butyl-4-hydroxybenzyl mercaptoacetate.
    [467] 1.8. Hydroxybenzylated malonates , for example dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, di-octadecyl-2- (3-tert-butyl 4-hydroxy-5-methylbenzyl) -malonate, di-dodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis- [4 -(1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.
    [468] 1.9. Aromatic hydroxybenzyl compounds such as 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3, 5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol .
    [469] 1.10. Triazine compounds such as 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-jade Tylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino) -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-dicyclo Hexyl-4-hydroxybenzyl) isocyanurate.
    [470] 1.11. Benzyl phosphonate , for example dimethyl-2,5-di-tert-butyl-4-hydroxybenzyl phosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, di Octadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzyl phosphonate, 3,5-di-tert Calcium salt of butyl-4-hydroxybenzyl-phosphonic acid monoethyl ester.
    [471] 1.12. Acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.
    [472] 1.13. Monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neo Pentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundanol , 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo [2.2.2] octane and β- (3,5 Esters of di-tert-butyl-4-hydroxyphenyl) -propionic acid .
    [473] 1.14. Monohydric or polyhydric alcohols such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol , Neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thia Undecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo- [2.2.2] octane and β- ( Ester of 5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid .
    [474] 1.15. Monohydric or polyhydric alcohols such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodi Ethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundanol, 3-thiapenta Decanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo- [2.2.2] octane and β- (3,5-dicyclohexyl Ester of -4-hydroxyphenyl) -propionic acid .
    [475] 1.16. Monohydric or polyhydric alcohols such as methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodi Ethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaundanol, 3-thiapenta Decanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo- [2.2.2] octane and 3,5-di-tert-butyl-4 Esters of hydroxyphenyl acetic acid .
    [476] 1.17. Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, for example N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionic acid) hexamethylene Diamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpyrropiionyl) trimethylenediamide, N, N'-bis (3,5-di-tert-butyl-4 -Hydroxy-phenylpropionyl) hydrazide, N, N'-bis [2- (3- [3,5-di-tert-butyl-4-hydroxy-phenyl] propionyloxy) ethyl] oxamide (Naugard R XL-1, supplied by Uniroyal).
    [477] 1.18. Ascorbic acid (vitamin C)
    [478] 1.19. Amine antioxidants such as N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-secondarybutyl-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-toluenesulfamoyl) -diphenylamine, N, N'-dimethyl-N, N'-di- Secondary butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1 -Naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamines such as p, p'-di-tert-octyldiphenylamine, 4-n-butyl Minophenol, 4-butyrylaminophenol, 4-nonanylamino-phenol, 4-dodecane oilaminophenol, 4-octadecane oilaminophenol, bis (4-methoxyphenyl) amine, 2,6-di- Tert-butyl-4-dimethylaminomethylphenol, 2,4'-di-aminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetramethyl-4,4' -Di-aminodiphenylmethane, 1,2-bis [(2-methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ' , 3'-dimethylbutyl) phenyl] amine, tertiary octylated N-phenyl-1-naphthylamine, mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamine, mono- and dialkylated nonyldiphenylamine Mixtures, mixtures of mono- and dialkylated nonyldiphenylamines, mixtures of mono- and dialkylated dodecyldiphenylamines, mixtures of mono- and dialkylated isopropyl / isohexylphenylamines, mono- and dialkylated tert-butyldiphenyl Mixture of amines, 2,3-di-hydro-3 , 3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mixture of mono and dialkylated tert-butyl / tert-octylphenothiazine, mixture of mono- and dialkylated tert-octyl-phenothiazine, N-allyl Phenothiazine, N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene.
    [479] 2. UV absorbers and light stabilizers
    [480] 2.1. 2- (2'-hydroxyphenyl) -benzotriazole , for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl- 2'-hydroxyphenyl) benzotriazole, 2- (5'-tertbutyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5 '-(1,1,3, 3-tetramethylbutyl) phenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl -2'hydroxy-5'methylphenyl) -5-chloro-benzotriazole, 2- (3'-secondarybutyl-5'-tert-butyl-2'hydroxyphenyl) benzotriazole, 2- (2'- Hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3 ', 5'-di-tertylamyl-2'-hydroxyphenyl) benzotriazole, 2- (3', 5'-bis- (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-octyloxycarbonylethyl) phenyl)- 5-Chloro-benzotriazole, 2- (3'-tert-butyl-5 '-[2- (2-ethylhexyloxy) -carbonylethyl] -2'-hydroxyphenyl) -5-chloro-benzo T Riazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl- 2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl ) Phenyl) benzotriazole, 2- (3'-tert-butyl-5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3 '-Dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3'-tertbutyl-2'-hydroxy-5'-(2-isooctyloxycarbonylethyl) phenylbenzo Triazole, 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; polyethylene glycol 300 and 2- [3'- Transesterification product of tert-butyl-5 '-(2-methoxycarbonylethyl) -2'-hydroxy-phenyl] -2H-benzotriazole; R is 3'-tert-butyl-4'-hydroxy- 5'-2H-benzotriazol-2-ylphenyl, 2- [2'-hydroxy-3 '-(α, α-dimethylbenzyl) -5'-(1,1,3,3-tet Methylbutyl) phenyl] benzotriazole, 2- [2'-hydroxy-3 '-(1,1,3,3-tetramethylbutyl) -5'-(α, α-dimethylbenzyl) phenyl] benzotria Sleepy .
    [481] 2.2. 2-hydroxybenzophenones , for example 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'- Trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
    [482] 2.3. Esters of unsubstituted or substituted benzoic acid , for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butyl-benzoyl) resorci Nol, benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, Octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
    [483] 2.4. Acrylates such as ethyl α-cyano-β, β-diphenylacrylate, isooctyl α-cyano-β, β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cya No-β-methyl-p-methoxy-cinnamate, butyl α-cyano-β-methyl-p-methoxy-cinnamate, methyl α-carbomethoxy-p-methoxy-cinnamate and N- ( β-carbomethoxy-β-cyanovinyl) -2-methylindolin.
    [484] 2.5. 2,2'-thio-bis [4- (1,1,3,2) with nickel compounds , for example with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, where appropriate 3-tetramethylbutyl) phenol] (such as 1: 1 or 1: 2 complex), nickel dibutyl dithiocarbamate, 4-hydroxy-3,5-di-tert-butyl benzyl phosphonic acid monoalkyl Nickel salts of esters (e.g. methyl esters or ethyl esters), nickel complexes of ketoximes (e.g. 2-hydroxy-4-methylphenyl undecylketoxim), 1-phenyl-4-lauro with additional ligands where appropriate Nickel Complex of Il-5-hydroxy Pyrazole.
    [485] 2.6. Oxamides , for example 4,4'-dioctyloxyoxananilide, 2,2'-diethoxyoxananilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxananilide, 2, 2'-didodecyloxy-5,5'-di-tert-butoxananilide, 2-ethoxy-2'-ethoxananilide, N, N'-bis (3-dimethylaminopropyl) oxaamide, 2- Ethoxy-5-tert-butyl-2'-ethoxananilide and mixtures thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, o- and p-methoxy- Mixtures of double substituted oxaanilides and mixtures of o- and p-ethoxy-disubstituted oxaanilides.
    [486] 2.7. 2- (2-hydroxyphenyl) -1,3,5-triazine , for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine , 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl ) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4- Dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2 -hydroxy-4-tridecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxy Phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxy-propoxy) Phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxy-propyloxy) phenyl ] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydrate Cy-phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxy- Propoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4,6-di Phenyl-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-hydroxy-propoxy) phenyl] -1,3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxy Phenyl) -6-phenyl-1,3,5-triazine, 2- {2-hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2-hydroxypropyloxy] phenyl}- 4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine.
    [487] 3. Metal deactivators such as N, N'-diphenyloxaamide, N-salicyl-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N ' -Bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyl dihydrazide, oxa Anilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N, N'-diacetyladifoyl dihydrazide, N, N'-bis (salicyloyl) oxalyl dihydrazide, N, N ' Bis (salicyloyl) thiopropionyl dihydrazide.
    [488] 4. Phosphites and phosphonites , for example triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, diss Tearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol depot Spite, bis (2,4,6-tris-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenyl Lene diphosphonite, 6-isooctyloxy-2,4,8,10-te Tri-tert-butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphosine, bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis (2,4 -Di-tert-butyl-6-methylphenyl) ethylphosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz [d, g] -1,3,2- Dioxaphosphosine, 2,2 ', 2 "-nitrilo [triethyltris (3,3', 5,5'-tetra-tert-butyl-1, 1'-biphenyl-2,2'-diyl ) Phosphite], 2-ethylhexyl (3,3 ', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite, 5-butyl-5- Ethyl-2- (2,4,6-tri-tert-butylphenoxy) -1,3,2-dioxaphosphyran.
    [489] Especially preferred are the following phosphites:
    [490] Tris (2,4-di-tert-butylphenyl) phosphite (Irgafos R 168, manufactured by Ciba-Geigy), tris (nonylphenyl) phosphite,
    [491]
    [492]
    [493]
    [494] 5. Hydroxylamines such as N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N , N-ditetedecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl- N-octadecylhydroxylamine, N, N-dialkylhydroxylamine derived from hydrogenated resin.
    [495] 6. Nitrons , eg N-benzyl-alpha-phenyl-nitron, N-ethyl-alpha-methyl-nitron, N-octyl-alpha-heptyl-nitron, N-lauryl-alpha-undecyl Nitron, N-tetradecyl-alpha-tridecyl-nitron, N-hexadecyl-alpha-pentadecyl-nitron, N-octadecyl-alpha-heptadecyl-nitron, N-hexadecyl-alpha- Derived from heptadecyl-nitron, N-octadecyl-alpha-petadecyl-nitron, N-heptadecyl-alpha-heptadecyl-nitron, N-octadecyl-alpha-hexadecyl-nitron, hydrogenated resinamine Nitron derived from N, N'-dialkylhydroxylamine.
    [496] 7. Thio synergists , for example dilauryl thiodipropionate or distearyl thiodipropionate.
    [497] 8. Peroxide degrading compounds , for example esters of β-thiodipropinic acid, such as lauryl, stearyl, myristyl or tridecyl esters, zinc salts of mercaptobenzimidazole or 2-mercaptobenzimidazole, di Butyldithiocarbamate zinc, dioctadecyl disulfide, pentaerythritol tetrakis (β-dodecylmercapto) propionate.
    [498] 9. Polyamide stabilizers , for example copper salts in combination with iodide and / or phosphorus compounds and salts of divalent manganese.
    [499] 10. Basic co-stabilizers , for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth metal salts of higher fatty acids Such as calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate, potassium palmitate, antimony pyrocatechol or tin pyrocatechol.
    [500] 11. Nucleating agents , for example inorganic substances (eg talc), metal oxides (eg titanium dioxide or magnesium oxide), preferably phosphates, carbonates or sulfates of alkaline earth metals; Organic compounds (mono- or polycarboxylic acids) and salts thereof such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; Polymeric compounds such as ionic copolymers ("ionomers"). 1,3: 2,4-bis (3 ', 4'-dimethylbenzylidene) sorbitol, 1,3: 2,4-di (paramethyldibenzylidene) sorbitol, and 1,3: 2,4-di Particular preference is given to (benzylidene) sorbitol.
    [501] 12. Fillers and reinforcing agents , for example powders of calcium carbonate, silicates, glass fibers, glass spheres, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood powder and other natural products or Fiber, synthetic fiber.
    [502] 13. Other additives , for example plasticizers, lubricants, emulsifiers, pigments, flow additives, catalysts, flow regulators, optical brighteners, flame retardants, antistatic agents and blowing agents.
    [503] 14. Benzofuranone and indolinones, for example US-A-4 325 863, US-A-4 338 244, US-A-5 175 312, US-A-5 216 052, US- A-5 252 643, DE-A-4 316 611, DE-A-4 316 622, DE-A-4 316 876, EP-A-0 589 839 or EP-A-0 591 102 As disclosed in the heading or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3- -(2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy]- Phenyl) benzofuran-2-one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butyl-benzofuran-2-one , 3- (3,4-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2-one, 3- (2,3-dimethylphenyl) -5,7-di-tert-butylbenzofuran-2 -On.
    [504] The weight ratio of the mixture of stabilizer to conventional additives according to the invention can be for example from 1: 0.1 to 1: 5.
    [505] The following examples illustrate the invention in more detail. All percentages and parts are by weight unless otherwise indicated.
    [506] Stabilizers and coadditives used in Examples 1-4 below :
    [507] Compound (13) :
    [508] ( R TINUVIN 770)
    [509]
    [510] Compound (14) :
    [511] ( R TINUVIN 765)
    [512]
    [513] Compound (49-a-1) :
    [514] ( R CYASORB UV3581)
    [515]
    [516] Compound (5-I) :
    [517]
    [518] PVA : Polyvinyl Alcohol
    [519] PA : Polyamide
    [520] PC : Polycarbonate
    [521] PET : Polyethylene Terephthalate
    [522] PBT : Polybutylene Terephthalate
    [523] PMMA : Polymethyl methacrylate
    [524] POM : Polyoxymethylene
    [525] TPU : Thermoplastic Polyurethane
    [526] PPE : Polyphenylene Ether
    [527] ASA : acrylic ester / styrene / acrylonitrile copolymer
    [528] SAN : Styrene / Acrylonitrile Copolymer
    [529] SMA : Styrene / maleic anhydride copolymer
    [530] Example 1 Light Stabilization in Polypropylene Homopolymer Films
    [531] 100 parts of unstabilized polypropylene powder (melt flow index: 3.8 g / 10 min, 230 ° C. and 2160 g) was added 0.05 part pentaerythryl-tetrakis {3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate}, 0.05 part tris {2,4-di-tert-butylphenyl} phosphite, 0.1 part Ca stearate, 0.25 part TiO 2 (anatase) and in Table 1 Homogenize at 200 ° C. for 10 min with the stabilizer mixture indicated. The material thus obtained is compression molded into a 0.5 mm thick film at 260 ° C. for 6 minutes between two aluminum foils in a laboratory compressor, which is immediately cooled to room temperature in a water cooled compressor. A 60 mm × 25 mm sample is cut from a 0.5 mm film and exposed at WEATHER-OMETER Ci 65 (black panel temperature 63 ± 2 ° C., no water spray).
    [532] Periodically, these samples are removed from the exposure apparatus and their carbonyl content is measured with an infrared spectrophotometer. The exposure time corresponding to the formation absorption of carbonyl 0.1 is a measure of the efficiency of the stabilizer mixture. The obtained values are summarized in Table 1 below.
    [533]
    [534] Example 2 Light Stabilization of Polypropylene Homopolymer Film
    [535] 100 parts of unstabilized polypropylene powder (melt flow index: 3.5 g / 10 min, 230 ° C. and 2160 g) was added to 0.05 part pentaerythritol-tetrakis {3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate}, 0.05 part tris {2,4-di-tert-butylphenyl} phosphite, 0.1 part Ca stearate, 0.25 part titanium dioxide (anatase) and in Table 2 Homogenize at 200 ° C. for 10 min with the indicated amount of light stabilizer and polar polymer. The material thus obtained is compression molded into a 0.5 mm thick film at 260 ° C. for 6 minutes between two aluminum foils in a laboratory compressor, which is immediately cooled to room temperature in a water cooled compressor. A 60 mm × 25 mm sample is cut from a 0.5 mm film and exposed at WEATHER-OMETER Ci 65 (black panel temperature 63 ± 2 ° C., no water spray).
    [536] Periodically, these samples are removed from the exposure apparatus and their carbonyl content is measured with an infrared spectrophotometer.
    [537] The exposure time (T 0.1 ) corresponding to the formation absorption of carbonyl 0.1 is a measure of the efficiency of the stabilizer mixture. The obtained values are summarized in Table 2 below.
    [538]
    [539]
    [540]
    [541] Example 3 Photostabilization of Polypropylene Homopolymer Film
    [542] 100 parts of unstabilized polypropylene powder (melt flow index: 3.8 g / 10 min, 230 ° C. and 2160 g) was added 0.05 part pentaerythryl-tetrakis {3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate}, 0.05 part tris {2,4-di-tert-butylphenyl} phosphite, 0.1 part Ca stearate, 0.25 part titanium dioxide (anatase) and in Table 3 Homogenize at 200 ° C. for 10 min with the indicated amount of light stabilizer, polar polymer and coadditive. The material thus obtained is compression molded into a 0.5 mm thick film at 260 ° C. for 6 minutes between two aluminum foils in a laboratory compressor, which is immediately cooled to room temperature in a water cooled compressor. A 60 mm × 25 mm sample is cut from a 0.5 mm film and exposed at WEATHER-OMETER Ci 65 (black panel temperature 63 ± 2 ° C., no water spray).
    [543] Periodically, these samples are removed from the exposure apparatus and their carbonyl content is measured with an infrared spectrophotometer.
    [544] The exposure time (T 0.1 ) corresponding to the formation absorption of carbonyl 0.1 is a measure of the efficiency of the stabilizer mixture. The obtained values are summarized in Table 3 below.
    [545]
    [546] Example 4 Photostabilization of Polypropylene Homopolymer Film
    [547] 100 parts of unstabilized polypropylene powder (melt flow index: 3.5 g / 10 min, 230 ° C. and 2160 g) was added 0.05 part of pentaerythritol-tetrakis in a brabender platograph. Di-tert-butyl-4-hydroxyphenyl) propionate}, 0.05 part tris {2,4-di-tert-butylphenyl} phosphite, 0.1 part Ca stearate, 0.25 part titanium dioxide (anatase) and in Table 4 Homogenize at 200 ° C. for 10 min with the indicated amount of light stabilizer and polar polymer. The material thus obtained is compression molded into a 0.5 mm thick film at 260 ° C. for 6 minutes between two aluminum foils in a laboratory compressor, which is immediately cooled to room temperature in a water cooled compressor. A 60 mm × 25 mm sample is cut from a 0.5 mm film and exposed at WEATHER-OMETER Ci 65 (black panel temperature 63 ± 2 ° C., no water spray).
    [548] Periodically, these samples are removed from the exposure apparatus and their carbonyl content is measured with an infrared spectrophotometer.
    [549] The exposure time (T 0.1 ) corresponding to the formation absorption of carbonyl 0.1 is a measure of the efficiency of the stabilizer mixture. The obtained values are summarized in Table 4 below.
    [550]
    权利要求:
    Claims (22)
    [1" claim-type="Currently amended] (A) hindered amine compound, and
    (B) a polar residue-containing polymer (A): (B) in a weight ratio of 20: 1 to 1:20,
    However, (1) component (B) is different from component (A), and does not contain the group of following general formula (I) or (II), and
    (2) Component (B) is different from the polymer having acidic hydrogen atoms, stabilizer mixture:
    (I)
    (II)
    In the above formula,
    G is hydrogen or methyl, and
    G 1 and G 2 are independently of each other hydrogen, methyl or combined to be substituent = 0.
    [2" claim-type="Currently amended] The stabilizer mixture of claim 1 wherein component (A) contains at least one group of formula (I) or (II):
    (I)
    (II)
    In the above formula,
    G is hydrogen or methyl, and
    G 1 and G 2 are independently of each other hydrogen, methyl or combined to be substituent = 0.
    [3" claim-type="Currently amended] The compound (A) according to claim 1, wherein the component (A) is represented by the following compounds (5), (13), (14), (23), (24), (36-a-1), (36-a-2) , (36-b-1), (36-b-2), (36-d), (49-a-1), (49-a-2), (49-c), (49-d) Stabilizer mixtures corresponding to compounds of (49-e), (63), (65), (69-a), (81), (82), (102), (105) or (106):
    5) 4-stearoyloxy-2,2,6,6-tetramethylpiperidine
    13) di (2,2,6,6-tetramethylpiperidin-4-yl) sebacate
    14) di (1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate
    23) Di (1,2,2,6,6-pentamethylpiperidin-4-yl) butyl (3,5-di-tert-butyl-4-hydroxybenzyl) malonate
    24) Di (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate
    36-a-1) 1,2,3,4-tetrakis [2,2,6,6-tetramethylpiperidin-4-yloxycarbonyl] butane
    36-a-2) bis [2,2,6,6-tetramethylpiperidin-4-yloxycarbonyl] -bis [tridecyloxycarbonyl] butane
    36-b-1) 1,2,3,4-tetrakis [1,2,2,6,6-pentamethylpiperidin-4-yloxycarbonyl] butane
    36-b-2) bis [1,2,2,6,6-pentamethylpiperidin-4-yloxycarbonyl] -bis [tridecyloxycarbonyl] butane
    36-d)

    49-a-1)

    49-a-2)

    49-c) 2- (2,2,6,6-tetramethylpiperidin-4-ylamino) -2- (2,2,6,6-tetramethylpiperidin-4-ylaminocarbonyl Propane
    49-d) 1,6-bis [N- (2,2,6,6-tetramethylpiperidin-4-yl) formylamino] hexane
    49-e)

    63) 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxodisspiro [5.1.11.2] henic acid
    65) 8-Acetyl-3-dodecyl-1,3,8-tria-7-7,7,9,9-tetramethylspiro [4.5] decane-2,4-dione
    69-a)






    [4" claim-type="Currently amended] The component (A) is according to claim 1, wherein the compound (76), (82-a), (84-1-a), (84-1-b), (84-2), or (91-1) , (92), (93), (96-I), (96-II), (97-I), (97-II), (99-I), (99-II), (99-III) Stabilizer mixtures corresponding to compounds of (100-A) or (101-I):



    Wherein m 4 is a number from 2 to 40

    Wherein m 4 is a number from 2 to 40

    Wherein m 4 is a number from 2 to 40

    Wherein m 11 * is as defined for m 11 and the radical R * is independently ethyl or 2,2,6,6-tetramethylpiperidin-4-yl, provided that 50% of the radicals R * Above is 2,2,6,6-tetramethylpiperidin-4-yl and the remaining radicals R * are ethyl)

    Wherein m 12 is a number from 2 to 40

    Wherein m 12 is a number from 2 to 40

    Wherein m 16 is a number from 2 to 50

    Wherein m 16 * is a number from 2 to 50

    Wherein m 17 is a number from 1 to 20

    Wherein m 17 is a number from 1 to 20

    Wherein G 11 is hydrogen or methyl and m 19 is a number from 1 to 25

    Wherein G 11 is hydrogen or methyl and m 19 is a number from 1 to 25

    Wherein G 11 is hydrogen or methyl and m 19 is a number from 1 to 25
    100-A) A product obtained by reacting an intermediate product obtained by reacting a polyamine of formula (100a) with cyanuric chloride with a compound of formula (100b):


    Wherein m 21 is a number from 1 to 20
    [5" claim-type="Currently amended] A compound according to claim 3, wherein component (A) is selected from compounds (5), (13), (14), (24), (49-a-1), (49-a-2) or (49-d). Stabilizer mixtures corresponding to the compounds.
    [6" claim-type="Currently amended] 4. Stabilizer mixture according to claim 3, wherein component (A) corresponds to compound (13).
    [7" claim-type="Currently amended] A compound according to claim 4, wherein component (A) is compound (76), (84-1-a), (84-1-b), (92), (93), (99-I), (100-A Or a stabilizer mixture corresponding to (101-I).
    [8" claim-type="Currently amended] The stabilizer mixture of claim 4, wherein component (A) corresponds to compound (76), (84-1-a), (84-1-b), (92) or (100-A).
    [9" claim-type="Currently amended] The stabilizer mixture of claim 1 wherein the weight ratio of component (A): (B) is from 5: 1 to 1: 5.
    [10" claim-type="Currently amended] The polymer of claim 1 wherein the polymer containing a polar moiety is
    (B-1) halogen-containing polymer,
    (B-2) polymers or derivatives thereof derived from α, β-unsaturated acids,
    (B-3) acrylonitrile / butadiene copolymer, acrylonitrile / alkyl acrylate copolymer, ethylene / acrylate copolymer, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide copolymer or acryl Nitrile / alkyl methacrylate / butadiene terpolymer,
    (B-4) polymers derived from unsaturated alcohols and amines or acyl derivatives or acetals thereof,
    (B-5) homopolymers or copolymers of cyclic ethers,
    (B-6) polyacetal,
    (B-7) polyphenylene oxide or a mixture of polyphenylene oxide and another polymer,
    (B-8) polyurethane,
    (B-9) polyamide or copolyamide,
    (B-10) polyurea, polyimide, polyamide-imide, polyetherimide, polyesterimide, polyhydantoin, polybenzimidazole or polyvinylimidazole,
    (B-11) polyester,
    (B-12) polycarbonate or polyester carbonate,
    (B-13) polysulfones, polyether sulfones or polyether ketones,
    (B-14) polymers derived from aldehydes and phenols, ureas or melamines,
    (B-15) dry or non-dry alkyd resin,
    (B-16) unsaturated polyester resin,
    (B-17) crosslinkable acrylic resin,
    (B-18) Alkyd resin, polyester resin or acrylate resin crosslinked with melamine resin, urea resin, isocyanate, isocyanurate, polyisocyanate or epoxy resin,
    (B-19) epoxy resin,
    (B-20) cellulose or chemically modified homologous derivatives thereof,
    (B-21) polyorgano siloxane,
    (B-22) polyvinyl formal (PVF),
    (B-23) poly (aryl-ether-ether-ketone) (PEEK), or
    Stabilizer mixtures which are copolymers of (B-24) vinyl aromatic monomers.
    [11" claim-type="Currently amended] The polymer according to claim 10, wherein the polymer containing a polar moiety is selected from (B-2), (B-4), (B-6), (B-7), (B-8), (B-9), ( B-11), a stabilizer mixture selected from the group (B-12) and (B-13).
    [12" claim-type="Currently amended] The method of claim 1, wherein component (B) is polyacrylate, polymethacrylate (PMA), polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), polyvinyl alcohol (PVA), polyvinyl acetate ( PVAc), polyoxymethylene (POM), polyphenylene ether (PPE), polyurethane, polyamide 3 (PA3), polyamide 6 (PA6), polyamide 11 (PA 11), polyamide 12 (PA 12) , Polyamide 66 (PA 66), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyacetic acid (PLA), polycarbonate (PC) or polyether sulfone (PES) or chemical formula A stabilizer mixture which is an aromatic aliphatic polysulfone (PSP) having a repeating unit of.
    [13" claim-type="Currently amended] The component (B) of claim 1, wherein the component (B) is a polyamide (PA), an acrylic ester / styrene / acrylonitrile copolymer (ASA), a styrene / acrylonitrile copolymer (SAN), a styrene / maleic anhydride copolymer ( SMA) or a stabilizer mixture which is a polyether amide.
    [14" claim-type="Currently amended] The method of claim 1, wherein component (B) is polymethacrylate (PMA), polymethyl methacrylate (PMMA), polyamide (PA), polyoxymethylene (POM), acrylic ester / styrene / acrylonitrile aerial. Stabilizer mixtures that are coalesced (ASA) or polyether amides.
    [15" claim-type="Currently amended] A compound according to claim 1, wherein component (A) is compound di (2,2,6,6-tetramethylpiperidin-4-yl) sebacate and component (B) is polyethylene terephthalate (PET), polyamide 6 (PA 6), polycarbonate (PC), polymethacrylate (PMA) or polymethyl methacrylate (PMMA), in particular polymethyl methacrylate (PMMA) and the weight ratio of components (A) :( B) Stabilizer mixture of 5: 1 to 1: 5.
    [16" claim-type="Currently amended] The stabilizer mixture of claim 15 wherein component (B) is polymethyl methacrylate (PMMA).
    [17" claim-type="Currently amended] The compound of claim 1, wherein component (A) is a compound di (2,2,6,6-tetramethylpiperidin-4-yl) sebacate or

    Of the compound: (wherein, m 4 is the number of 2 to 40) and and component (B) is polyamide (PA), polyoxymethylene (POM) or polyether amide the stabilizer mixture.
    [18" claim-type="Currently amended] 2. The stabilizer mixture of claim 1, further comprising, as additional component (XX), an organic salt of Ca, an inorganic salt of Ca, Ca oxide, or Ca hydroxide.
    [19" claim-type="Currently amended] 2. Stable according to claim 1, further comprising as an additional component (XXX) an organic salt of Zn, an inorganic salt of Zn, a Zn oxide, a Zn hydroxide, an organic salt of Mg, an inorganic salt of Mg, an Mg oxide or an Mg hydroxide. Topical mixtures.
    [20" claim-type="Currently amended] A composition comprising a polyolefin and a stabilizer mixture according to claim 1.
    [21" claim-type="Currently amended] The composition of claim 20 wherein the polyolefin is polyethylene or polypropylene or a copolymer of polyethylene or polypropylene.
    [22" claim-type="Currently amended] A method for stabilizing a polyolefin from decomposition due to light, heat or oxidation, comprising incorporating the stabilizer mixture according to claim 1 in the polyolefin.
    类似技术:
    公开号 | 公开日 | 专利标题
    JP5405400B2|2014-02-05|Synergistic combination of UV absorbers
    KR100316724B1|2002-02-28|Hydroxyphenyl-S-triazine
    AU767538B2|2003-11-13|Synthetic polymers comprising additive blends with enhanced effect
    US6117995A|2000-09-12|Preparation of sterically hindered amine ethers
    KR100778769B1|2007-11-27|Transparent polymer articles of low thickness
    NL1019532C2|2002-09-06|Improved weather resistance of flame-resistant polyolefin.
    US5869588A|1999-02-09|Polymeric compounds derived from 2-hydroxy-phenyl-s-triazines substituted with ethylenically unsaturated moieties
    ES2318059T3|2009-05-01|Ignifugant compositions.
    CA2187708C|2007-06-05|Stabiliser combinations for chlorine-containing polymers
    AU2008340442B2|2013-09-26|Flame retardant compositions comprising sterically hindered amines
    US6916867B2|2005-07-12|Synergistic mixtures of UV-absorbers in polyolefins
    ES2203344B1|2005-07-16|"mixing stabilizers".
    EP0690094B1|2002-08-21|Use of sterically hindered amines in combination with a metal oxide or hydroxide to improve the light stabilitiy and pesticide resistance of polyolefin or olefin copolymer films
    CA2445617C|2011-12-06|Composition and process for enhancing bio-mass production in greenhouses
    AU2004275997B2|2010-07-22|Stabilization of photochromic systems
    KR101368176B1|2014-03-14|Stabilizer composition for polymers
    EP1668073B1|2009-04-29|Flame retardant compositions
    EP0782994B1|2003-02-05|Block oligomers containing 2,2,6,6-tetramethyl-4-piperidyl groups as stabilizers for organic materials
    NL1002950C2|1998-05-27|Stabilizer combination for synthetic organic polymers.
    ES2276075T3|2007-06-16|Stabilization of polyolefine in permanent contact with clorated water.
    ES2276335T3|2007-06-16|Flame delay polylactic acid.
    AU2003242560B2|2009-04-30|Stabilized articles
    CN100429259C|2008-10-29|Stabilizer mixtures for polyolefins
    ES2297438T3|2008-05-01|Highly compatible and non-migration polymer uv uv absorber.
    EP0728806B1|1998-03-25|Synergistic stabiliser mixture
    同族专利:
    公开号 | 公开日
    IN2002CH01489A|2005-01-28|
    PT1263855E|2008-04-16|
    EP1263855B1|2008-03-12|
    WO2001062836A1|2001-08-30|
    CA2400413A1|2001-08-30|
    US6869992B2|2005-03-22|
    DE60133181T2|2009-03-12|
    AU3376401A|2001-09-03|
    EP1263855A1|2002-12-11|
    KR100727524B1|2007-06-14|
    ES2301528T3|2008-07-01|
    AT388988T|2008-03-15|
    US20030069337A1|2003-04-10|
    JP4733898B2|2011-07-27|
    MX235505B|2006-04-05|
    IN205902B|2007-06-29|
    RU2002123336A|2004-01-20|
    BR0108512B1|2012-07-24|
    DE60133181D1|2008-04-24|
    CA2400413C|2010-01-12|
    BR0108512A|2002-12-17|
    CN100429259C|2008-10-29|
    RU2263688C2|2005-11-10|
    JP2003524047A|2003-08-12|
    CN1404501A|2003-03-19|
    MXPA02008161A|2002-11-29|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2000-02-22|Priority to EP00810149
    2000-02-22|Priority to EP00810149.5
    2001-02-15|Application filed by 시바 스폐셜티 케미칼스 홀딩 인코포레이티드
    2001-02-15|Priority to PCT/EP2001/001685
    2002-10-07|Publication of KR20020075922A
    2007-06-14|Application granted
    2007-06-14|Publication of KR100727524B1
    优先权:
    申请号 | 申请日 | 专利标题
    EP00810149|2000-02-22|
    EP00810149.5|2000-02-22|
    PCT/EP2001/001685|WO2001062836A1|2000-02-22|2001-02-15|Stabilizer mixtures for polyolefins|
    [返回顶部]